EP0704318A1 - Méthode d'enregistrement pour matériau sensible à la chaleur - Google Patents

Méthode d'enregistrement pour matériau sensible à la chaleur Download PDF

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Publication number
EP0704318A1
EP0704318A1 EP94115226A EP94115226A EP0704318A1 EP 0704318 A1 EP0704318 A1 EP 0704318A1 EP 94115226 A EP94115226 A EP 94115226A EP 94115226 A EP94115226 A EP 94115226A EP 0704318 A1 EP0704318 A1 EP 0704318A1
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EP
European Patent Office
Prior art keywords
silver
imaging material
image
thermal
imagewise
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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EP94115226A
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German (de)
English (en)
Inventor
Piero Ramello
Adriano Gribaudo
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3M Co
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Minnesota Mining and Manufacturing Co
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Publication date
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Priority to EP94115226A priority Critical patent/EP0704318A1/fr
Priority to JP24941895A priority patent/JPH08179459A/ja
Publication of EP0704318A1 publication Critical patent/EP0704318A1/fr
Withdrawn legal-status Critical Current

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    • 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
    • G03C1/49836—Additives
    • G03C1/49845—Active additives, e.g. toners, stabilisers, sensitisers
    • G03C1/49854—Dyes or precursors of dyes
    • 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
    • G03C2200/00—Details
    • G03C2200/22—Dye or dye precursor

Definitions

  • the present invention relates to a novel imaging method for thermal sensitive materials, more precisely to an imaging method comprising (1) forming a primary image by the imagewise thermal exposure of thermographic materials comprising a source of reducible metal ions in reaction proximity with thermal reducing compounds, and (2) uniformly processing the primary image during and/or subsequent to said imagewise thermal exposure.
  • Imaging elements that can be imagewise exposed by means of light or heat are well known.
  • Silver halide photographic elements are the most representative elements of the class of light-sensitive materials. They usually require a further wet development processing in order to render visible the latent image formed during light exposure.
  • the photosensitive silver halide films are processed by low intensity non-imagewise secondary photoexposure, as described in Research Disclosure, December 1989, Item 308119, Paragraph XXVII.
  • photosensitive imaging elements comprising silver halides and involving dry processing
  • dry silver films dry silver films
  • photothermographic elements Dry silver films are exposed by means of actinic radiation to form a latent image, which is then amplified by means of heat.
  • photothermographic materials have been described by J.W.Carpenter and P.W.Lauf in their review of "Photothermographic Silver Halide Systems", Research Disclosure, No. 17029, June 1978.
  • pre-photothermographic elements described in US 3,764,329, US 3,802,888, US 3,816,132 and US 4,113,496 comprises, instead of silver halides, some particular halide anion thermal precursors, which allow the formation of silver halide when the elements are uniformly heated before imagewise photoexposure. These elements can be daylight handled before thermal activation.
  • thermosensitive recording materials are the so called thermosensitive recording materials, widely employed in facsimile machines, labels, tickets, charts for recording the output of medical or scientific monitoring apparatus, and the like.
  • Direct thermal and thermal mass or dye transfer materials are the most representative examples of this class.
  • the recording material comprises a support carrying a coating of a thermally-sensitive composition comprising a color former, usually a substantially colorless electron donating dye precursor, and a color developer, usually an electron accepting compound.
  • Heat is imagewise applied to the element by means of a thermal head, a thermal pen or a laser beam, and upon said imagewise applied heating, the color former instantaneously reacts with the color developer to form a recorded image.
  • each of the above mentioned classes of imaging elements has of some disadvantages.
  • the conventional wet processed silver halide photographic materials have a high environmental impact due to their processing chemistry; the photothermographic materials give lower image fastness and limited optical density (for example, their processed image has still some unreacted silver halide and unexposed areas undergo to blackening from photoreduction of silver ions, giving a so called "print-out").
  • the direct thermal and thermal mass or dye transfer materials require high imaging energy and give limited image fastness and optical density as well.
  • thermographic materials comprising NIR dyes and a reducing agent for silver ions is an effective laser diode addressable imaging system.
  • the material disclosed in EP 582,144 does not comprise silver halides and is imaged electronically using a simple laser scanner that requires no post-thermal processing step for the media.
  • a disadvantage of the above method relates to the poor image tone obtained and the low stability of the silver image, as well as the high laser energy required to expose and develop the photothermographic material.
  • the object of the present invention is to provide a new method for obtaining images from conventionally known imaging elements overcoming some of the above mentioned disadvantages, so providing a silver image having good black hue and good fastness, with a reduction of the thermal energy for the imagewise exposure.
  • primary image means a visible and/or non-visible “latent image” that may be processed to improve its characteristics (optical density, hue, fastness and the like) to obtain the desired final image.
  • the present invention also relates to a method for obtaining an image wherein a imaging material comprising at least one heat-reducible metal compound in reaction proximity with a reducing compound is imagewise exposed to heat, and developed by means of uniform processing method during and/or subsequent to said imagewise thermal exposure.
  • the present invention relates to a method for obtaining an image wherein an imaging material, comprising at least one heat-reducible metal compound in reaction proximity with a reducing compound is imagewise exposed to heat, and developed by means of uniform processing during and/or subsequent to said imagewise thermal exposure.
  • any known imaging material which comprises reducible metal ions can be processed according to the claimed method.
  • any known silver halide material can be useful to describe the method of the present invention, including conventional photosensitive silver halide films, conventional photothermographic materials (dry silver materials), prephotothermographic materials (as described, for example, in US 3,764,329, US 3,802,888, US 3,816,132, US 4,113,496), and direct thermal materials (as described in EP 582,144).
  • conventional photosensitive silver halide elements are employed in the method of the present invention, both the imagewise thermal exposure and the processing must be performed in the dark or in safety light, to prevent high Dmin formation due to the elements' intrinsic photosensitivity.
  • thermographic materials which are not sensitive to light. These latter materials can be exposed and processed in daylight.
  • thermo material means any imaging element which can be imagewise exposed by means of heat, that is a thermal-sensitive material, and developed by means of uniform processing, preferably by means of a uniform thermal exposure.
  • thermal-sensitive material any imaging element which can be imagewise exposed by means of heat, that is a thermal-sensitive material, and developed by means of uniform processing, preferably by means of a uniform thermal exposure.
  • the heat reducible metal compounds which can be used in the present invention can be any metal compound which can form a catalytic latent image when heated for an ultra short time (from 0.01 microsecond to 100 millisecond, preferably from 0.1 microseconds to 10 milliseconds), at high temperatures (from 100 to 1200°C) in the presence of a reducing agent, said latent image being further processable to form the desired final image.
  • Any material comprising a support having at least one layer of a binder dispersion of a reducible source of metal ions which can be imagewise exposed to heat to obtain a primary image which in turn can be amplified by means of uniform processing can be useful in the method of the present invention.
  • Metals which can be useful for the purpose of the present invention are, for example, Au, Ag, Cu, Pd, Rh, and the like.
  • Organic or inorganic silver salts have been demonstrated particularly useful in the method of the present invention, but any other organic or inorganic metal salt, or combination thereof, which can be reduced to metal specks by means of heat can be useful.
  • the selection of a specific metal salt is mainly related to the tone and hue of the resulting metal, its redox potential, its cost and availability.
  • Other metal ions having, per se, a low catalytic redox activity such as, for example, Ca, Mg, Zn, Bi, and the like, may be used as promoters for the primary image formation and/or as processing accelerator
  • thermographic material useful in the method of the present invention may be constructed of one or more layers on at least one substrate.
  • Single layer constructions may contain the metal source compound, the developer, the toner and binder as well as other additional materials such as coating aids and other adjuvants.
  • Multiple-layer constructions can contain the metal source in one emulsion layer and some of the other ingredients in the same or other layers.
  • a protective layer is usually coated as a top-layer to protect the sensitive layers from damage due to handling during storing, exposure, and/or development.
  • intermediate layers can be interposed between the layer comprising the metal source and the layer comprising the toner, the developer or both.
  • Multiple-layer constructions can be realized also in order to separate the layer comprising the final image from the layer(s) comprising developer and/or other additives after processing. For this purpose a multilayered structure comprising all the required ingredients in different layers can be coated on two different support bases, which can be separated at the end of the imaging process.
  • both the "primary image” formation and/or its uniform processing involve the thermal diffusion transfer of at least one meltable ingredient so that also the so called “position latent images” are possibly formed and have a significant role in the imaging control.
  • the preferred silver source compound may be any material which contains a reducible source of silver ions.
  • Inorganic silver salts such as silver halide can be used, but silver salts of organic acids, particularly long chain (9 to 30, preferably 15 to 28 carbon atoms) fatty carboxylic acids are preferred.
  • Complexes of organic or inorganic silver salts wherein the ligand has a high stability constant between 4.0 and 10.0 are also desirable.
  • the silver source material constitutes from about 5 to 90 percent by weight of the imaging layer. The additional layers in a multilayer construction would not greatly affect the percentage of the silver source material desired in the single imaging layer.
  • Particularly suitable organic silver salts include silver salts of organic compounds having a carboxy group.
  • Preferred examples thereof include a silver salt of an aliphatic carboxylic acid and a silver salt of an aromatic carboxylic acid.
  • Preferred examples of the silver salts of aliphatic carboxylic acids include silver behenate, silver stearate, silver oleate, silver laurate, silver caprate, silver myristate, silver palmitate, silver maleate, silver fumarate, silver tartarate, silver furoate, silver linoleate, silver butyrate, silver versatates and silver camphorate, mixtures thereof, etc.
  • Preferred examples of the silver salts of aromatic carboxylic acid and other carboxyl group-containing compounds include silver benzoate, a substituted silver 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, a silver salt of 3-carboxymethyl-4-methyl-4-thiazoline-2-thione or the like as described in U.S. Pat. No. 3,785,830, and a silver salt of an aliphatic carboxylic acid containing a thioether group as described in U.S. Pat. No. 3,330,663, etc.
  • Silver salts of compounds containing mercapto or thione groups and derivatives thereof can be used.
  • Preferred examples of these compounds include a silver salt of 3-mercapto-4-phenyl-1,2,4-triazole, a silver salt of 2-mercaptobenzimidazole, a silver salt of 2-mercapto-5-aminothiadiazole, a silver salt of 2-(2-ethylglycolamido) benzothiazole, a silver salt of thioglycolic acid such as a silver salt of a S-alkyl thioglycolic acid (wherein the alkyl group has from 12 to 22 carbon atoms) as described in Japanese patent application No.
  • a silver salt of a dithiocarboxylic acid such as a silver salt of dithioacetic acid, a silver salt of thioamide, a silver salt of 5-carboxylic-1-methyl-2-phenyl-4-thiopyridine, a silver salt of mercaptotriazine, a silver salt of 2-mercaptobenzoxazole, a silver salt as described in U.S. Pat. No.
  • a silver salt of 1,2,4-mercaptothiazole derivative such as a silver salt of 3-amino-5-benzylthio-1,2,4,-thiazole
  • a silver salt of thione compound such as a silver salt of 3-(2-carboxyethyl)-4-methyl-4-thiazoline-2-thione as disclosed in U.S. Pat. No. 3,201,678.
  • a silver salt of a compound containing an imino group can be used.
  • Preferred examples of these compounds include a silver salt of benzothiazole and a derivative thereof as described in Japanese patent publications Nos. 30270/69 and 18146/70, for example, a silver salt of benzothiazole such as silver salt of methylbenzotriazole, etc., a silver salt of a halogen substituted benzotriazole, such as a silver salt of 5-chlorobenzotriazole, etc., a silver salt of 1,2,4-triazole, of 1-H-tetrazole as described in U.S. Pat. No. 4,220,709, a silver salt of imidazole and an imidazole derivative, and the like.
  • silver half soaps of which an about equimolar blend of silver behenate and behenic acid, prepared by precipitation from aqueous solution of the sodium salt of commercial behenic acid and about 14.5 percent silver, represents a preferred example.
  • Transparent sheet materials made on transparent film backing require a transparent coating and for this purpose the silver behenate full soap, containing less than about 5 percent of free behenic acid and about 20-25% silver may be used.
  • thermographic material can contain additives to improve the reducing action of heat, to improve the tone of the developed metal, and the like.
  • thermographic material additionally comprises at least one reducing agent (developer), and, according to a preferred embodiment, at least one toner, dispersed in a binder.
  • developer reducing agent
  • toner dispersed in a binder
  • the reducing agent for silver ion may be any material, preferably organic material, which will reduce silver ion to metallic silver.
  • Conventional photographic developers such as phenidone, hydroquinones, and catechol are useful but hindered phenol reducing agents are preferred.
  • the reducing agent should be present as 1 to 10 percent by weight of the imaging layer. In a two-layer construction, if the reducing agent is in the second layer, slightly high proportions, of from about 2 to 15 percent tend to be more desirable.
  • amidoximes such as phenylamidoxime, 2-thienylamidoxime and p-phenoxy-phenylamidoxime, azine, e.g., 4-hydroxy-3,5-dimethoxy-benzaldehyde azine; a combination of aliphatic carboxylic acid aryl hydrazides and ascorbic acid, such as 2,2-bis(hydroxymethyl)propionyl- ⁇ -phenyl hydrazide in combination with ascorbic acid; a combination of polyhydroxybenzene and hydroxylamine, a reductone and/or a hydrazine, e.g., a combination of hydroquinone and bis(ethoxyethyl)hydroxylamine, piperidinohexose reductone or formyl-4-methylphenyl hydrazine, hydroxamic acids such as phenyl-hydroxamic acid, p-hydroxyphenyl hydroxamic acid,
  • Toners can have several roles, such as, for example, silver salt wetting, the control of pigment formation speed, pigment dispersion degree, and image hue.
  • the materials may be present, for example, in amounts from 0.1 to 10 percent by weight of all silver bearing components. Toners are well known materials in the photothermographic art as shown in U.S. Pat. No. 3,080,254; 3,847,612 and 4,123,282.
  • toners examples include phthalimide and N-hydroxy-phthalimide; cyclic imides such as succinimide, pyrazoline-5-ones, and a quinazolinone, 3-phenyl-2-pyrazoline-5one, 1-phenylurazole, quinazoline and 2,4-thiazolidinedione; naphthalimides, e.g., N-hydroxy-1,8-naphthalimide; cobalt complexes, e.g., cobaltic hexamine trifluoroacetate; mercaptans as illustrated by 3-mercapto-1,2,4-triazole, 2,4-dimercaptopyrimidine, 3-mercapto-4,5-diphenyl-1,2,4-triazole and 2,5-dimercapto-1,3,4-thiadiazole; N-(aminomethyl)aryl dicarboximides, e.g.
  • N-dimethylaminomethyl)-phthalimide and N-(dimethylaminomethyl)-naphthalene-2,3 di-carboximide; and a combination of blocked pyrazoles, isothiuronium derivatives and certain photobleach agents, e.g., a combination of N,N'-hexamethylene bis-(1-carbamoyl-3,5-dimethylpyrazole), 1,8-(3,6-diazaoctane)-bis-(isothiuronium)-trifluoroacetate and 2-(tribromomethylsulfonyl benzo-thiazole); and merocyanine dyes such as 3-ethyl-5-[(3-ethyl-2-benzo-thiazolinylidene)-1-methylethylidene]-2-thio-2,4-oxazolidinedione; phthalazinone, phthalazinone derivatives or metal salts or these derivatives such as
  • thermographic material useful in the method of the present invention can contain compounds absorbing the infrared portion of the electromagnetic spectrum, preferably in the range of from 600 to 1500 nm, more preferably in the range of from 700 to 1100 nm.
  • Useful compounds for this purpose are organic dyes, such as, merocyanines, cyanines and especially tricarbocyanines.
  • organic dyes such as, merocyanines, cyanines and especially tricarbocyanines.
  • infrared absorbing dyes are described for example in US Pat. Nos. 3,457,078, 3,619,154, 3,682,630, 3,690,891, 3,695,888, 4,030,932 and 4,367,800.
  • the preferred classes of dyes are the tricarbocyanines such as 3,3'-dialkylthia-tricarbocyanines, thiatricarbocyanines (especially with rigidified chains), selenotricarbocyanines, and enamine tricarbocyanines.
  • "Tricarbocyanine” is a term used in the art to include dyes having an amidinium-ion chromophoric system (see Mees and James above, page 201). Tricarbocyanine infrared absorbing dyes are also described in US Patent Nos. 4,536,473, 4,959,294, 5,061,618, 4,619,892, 3,506,655, 3,552,974, 3,623,881 and 3,758,461.
  • Preferred infrared absorbing dyes are represented by the following general formula: wherein, Z1 and Z2 each independently represents the atoms necessary to complete a azole nucleus or a thiazole nucleus or an oxazole nucleus or a selenazole nucleus, Q represents the atoms necessary to complete a 5- or 6-membered carbocyclic ring, R1 and R2 each independently represents a alkyl group, R3 represents hydrogen, alkyl groups of 1 to 4 carbon atoms, aryl groups, cyano, halogen or - NR4R5, wherein R4 and R5 each independently represents alkyl groups of 1 to 6 carbon atoms or aryl groups or together represent the non-metallic atoms necessary to form a 5- or 6-membered heterocyclic ring, X ⁇ represents an anion, and n represents an integer of 1 to 2, provided that n is 1 when the dye forms an intramolecular salt.
  • the described chemical material includes the basic group and that group with conventional substitution.
  • moiety is used to describe a chemical compound or substituent only an unsubstituted chemical material is intended to be included.
  • the binder may be selected from any of the well-known natural or synthetic resins such as gelatin, polyvinyl acetals, polyvinyl chloride, polyvinyl acetate, cellulose acetate, polyolefins, polyesters, polystyrene, polyacrylonitrile, polycarbonates, and the like. Copolymers and terpolymers are of course included in these definitions.
  • the preferred polymer is polyvinyl butyral, butylethyl cellulose, methacrylate copolymers, maleic anhydride ester copolymers, polystyrene, and butadiene-styrene copolymers.
  • these polymers may be used in combination of two or more thereof.
  • Such a polymer is used in an amount sufficient to carry the components dispersed therein, that is, within the effective range of the action as the binder.
  • the effective range can be appropriately determined by one skilled in the art.
  • a preferable ratio of the binder to the organic silver salt ranges from 15:1 to 1:15, and particularly from 8:1 to 1:8.
  • Thermographic emulsions of the invention can be coated on a wide variety of supports.
  • Typical supports include polyester film, subbed polyester film, poly(ethylene terephthalate) film, cellulose nitrate film, cellulose ester film, poly(vinyl acetal) film, polycarbonate film and related or resinous materials, as well as glass, paper, metal and the like.
  • a flexible support is employed, especially a paper support, which can be partially acetylated or coated with baryta and/or an ⁇ -olefin polymer, particularly a polymer of an ⁇ -olefin containing 2 to 10 carbon atoms such as polyethylene, polypropylene, ethylene-butene copolymers and the like.
  • Thermographic emulsions of this invention can be coated by various coating procedures including dip coating, air knife coating, curtain coating, or extrusion coating using hoppers of the type described in Benguin, U.S. Pat. No. 2,681,294. If desired, two or more layers may be coated simultaneously by the procedures described in Russell, U.S. Pat. No. 2,761,791 and Wynn British Patent No. 837,095.
  • thermographic material is imagewise exposed to heat in order to promote the primary image formation, which will be further processed to obtain the final image.
  • the thermal exposure can be performed by conventional thermal printing head.
  • the more appropriate burn profile can be optimized for each particular composition of the thermographic material by a man skilled in the art.
  • thermographic material useful in the method of the present invention can contain compounds absorbing the infrared portion of the electromagnetic spectrum.
  • the imagewise exposure could also be performed by an infrared laser source. It must be highlighted that the role of the infrared adsorbing dye is to convert the infrared radiation to heat, and not to photosensitize the thermographic material to infrared light.
  • the thermographic material containing the infrared dye useful in the method of the present invention must be substantially insensitive to infrared light.
  • thermographic material is not able to give a latent image (i.e.,the primary image) upon exposure to an infrared emitting laser diode with a power lower than 10,000 erg/cm2 (0.001J/cm2).
  • Said imagewise thermal exposure, producing the "primary image” can also be done by "contact copy” (where the infrared radiation is imagewise transmitted by a reverse image pattern in vacuum contact with thermal film) by using unmodulated laser scanner emitting high intensity uniform radiation absorbed both by the pattern image and by the thermosensitive film.
  • the thermally sensitive side of thermal film should preferably contact the counterside of the pattern support.
  • thermographic material employed in their conventional aqueous processing line.
  • Other thermographic materials such as dry silver materials and direct thermal materials can be processed by uniform exposure to heat.
  • Pre-photothermographic materials can be processed by heat combined or not with photoexposure.
  • the preferred processing method when effective, includes development by uniform exposure to heat.
  • the thermal processing of the primary image may be done by any conventional thermal processing method capable of supplying uniform heat to the film surface (provided that the time-temperature threshold conditions for fogging the Dmin areas is not exceeded).
  • the processing heat may be supplied by contacting the film with hot surfaces (plates, rollers, ribbons..), by irradiation, by hot fluids uniform blowing, including gas or fluidized solid suspensions, by dipping in hot fluids, and the like.
  • thermographic material is imagewise exposed to heat by means of a thermal printing head or an infrared laser.
  • the thermographic material is exposed for an ultrarapid period of time, in the order of from 0.01 microsecond to 100 millisecond, preferably from 1 microsecond to 10 milliseconds, to a source of heat, which is able to locally increase the temperature of the thermographic material to a value of from about 100° to 1200°C.
  • the elementary or smallest imaging spot may range from about 100 ⁇ m2 for laser exposures, up to the thermal printhead elementary dot dimensions, the areas of which are an obvious function of the selected head addressability (dpi), but being usually smaller than 10000 ⁇ m2.
  • the ultrarapid heating of the thermographic material promotes the formation of the "primary image” or "latent image”.
  • the primary image has a high redox catalytic action.
  • the primary image can be visible or not visible, depending upon the amount of energy employed during exposure and the nature of film ingredients.
  • the partially and imagewise developed transient thermal latent image becomes partially visible is the real "primary image" of the thermographic materials that, however, maintains a very high catalytic activity and must be further amplified and stabilized by the uniform and controlled thermal processing of the present invention method in a relatively low temperature range (65-140°C).
  • the transient latent image is much more amplified during the imagewise thermal exposure and may generate very dense and almost black "primary images". Said very dense and almost black primary images are, however, still too unstable and need further non-imagewise thermal amplification to become denser, blacker and faster as well.
  • the conditions of the thermal development can vary upon the composition of the thermographic material employed.
  • the thermal fogging threshold for the formation of the image can be identified by a time to temperature diagram.
  • a time-temperature diagram can be obtained for each thermographic element by several ways, but it is convenient to use the very same apparatus that will be used for the thermal processing, because the rapidity of the heat transmission to the film is a very important factor.
  • the threshold exposures are identified also for higher temperatures and shorter time couples until enough dots are found to interpolate the exposure t-T line.
  • thermographic element After the imagewise exposure of a given thermographic element, its primary image will be processed in the desired range of t-T processing exposure space slightly below said thermal threshold line and by using the very same processing apparatus used for threshold identification.
  • a processing temperature is selected to adjust the desired length of the exposure-processing apparatus and to optimize imaging consistency.
  • the preferred thermographic elements have a thermal threshold in the range from 65°C to 130° C in the time range of from 1 to 100 seconds, preferably, from 75°C to 110°C in the time range of from 5-80 seconds, and more preferably from 85°C to 100°C in the time range of from 10-60 seconds.
  • the novel imaging method of the present invention requires a limited imaging energy, whereas the final image is completed afterwards by the imagewise catalyzed thermal reduction of the silver ions remaining in the image areas and by involving cheaper uniform processing energy.
  • the processing of the "primary image” is preferably done "in line” with the exposure, by putting the processing section just after the exposure section of a continuous exposure-processing device so that the total imaging time is compressed by overlapping.
  • the processing can also be performed concurrently with the formation of the primary image if the thermographic element is uniformly preheated to a temperature just below the thermal threeshold described above. In this case as soon as the primary image is formed by the action of the thermal image-wise exposure, the catalytic action of the metal specks and the action of the heating allow the formation of the final image.
  • Thermographic elements including the those described in EP 582,144 are particularly preferred for the scope of the present invention.
  • the "in line processing" is particularly convenient when the present invention imaging method is applied to said non-photosensitive thermographic elements. In fact, in this case the printing productivity is surprisingly higher than the one obtainable by employing the EP 582,144 method with the very same films (i.e by omitting the processing of the present invention method).
  • the processing may be done separately and later, because the "primary image" of the present invention method has a significant stability and may be processed with negligible final image differences if kept for several days at room temperature. It must be also stressed that the amplification of the "primary image" by said thermal uniform processing is not dependent on the imagewise thermal exposure conditions so that it allows an important second chance in controlling the final image characteristics with a high degree of freedom (both for the imaging and the processing conditions) and with high consistency. For these reasons, the present invention, in comparison with the prior art, allows improved and better controlled final image characteristics including hue, optical density, sensitometry and, overall, significantly higher image fastness.
  • thermographic film 1 was prepared according to the following procedure.
  • a paper support base was coated with a layer of thermosensitive composition comprising 8g of a 26% silver behenate dispersion in 6% MowitalTM B60H in acetone/mek (1/9) and 0.033 moles of cupric behenate per mole of silver behenate, 0.35g of IrganoxTM 2246 developer, and 0.1g of phthalazinone toner, at a wet coating gap of 50 ⁇ m with a Erichsen precision coater.
  • a protective layer comprising 8g of 6% MowitalTM B60H solution in acetone/mek (9/1) was top-coated at a wet coating gap of 30 ⁇ m.
  • thermographic film 2 was prepared according to the same procedure of sample 1, but an infrared dye IR-1 was additionally present in the coating composition of the thermosensitive layer.
  • thermographic film 3 was prepared according to the following procedure.
  • a paper support base was coated with a first layer comprising a composition of 8g of a 26% silver behenate dispersion in 6% MowitalTM B60H in acetone/mek (1/9) and 0.033 moles of cupric behenate per mole of silver behenate (silver soap), at a wet coating gap of 50 ⁇ m with a Erichsen precision coater.
  • a second layer was coated on the first layer with a coating composition comprising 0.35g of IrganoxTM 2246 developer and 0.1g of phthalazinone toner dispersed in 8g of a 6% MowitalTM B60H solution in acetone/mek (9/1) (binder), at a wet coating gap of 30 ⁇ m.
  • a protective layer comprising 8g of 6% MowitalTM B60H solution in acetone/mek (9/1) was top-coated at a wet coating gap of 30 ⁇ m.
  • thermographic film 4 was prepared according to the same procedure of sample 3, but the order of coating of the first and second layer was inverted.
  • thermographic film 5 was prepared according to the same procedure of sample 3, but the first layer composition comprises 0.1g of toner dispersed in the binder and the second layer comprises the silver soap and 0.25g of developer.
  • the wet coating gap of the second layer was 50 ⁇ m.
  • thermographic film 6 was prepared according to the same procedure of sample 3, but the first layer comprises the silver soap and the developer, and the second layer comprises the toner dispersed in the binder.
  • thermographic film 7 was prepared according to the same procedure of sample 3, but the first layer comprises the developer dispersed in the binder, and the second layer comprises the toner dispersed in the silver soap. The wet coating gaps of the first and second layer were inverted.
  • thermographic film 8 was prepared according to the same procedure of sample 3, but the first layer comprises the toner dispersed in the silver soap, and the second layer comprises the developer dispersed in the binder.
  • thermographic film 9 was prepared according to the same procedure of sample 3, but the first layer comprises 0.25g of developer dispersed in the silver soap, and the second layer comprises the toner dispersed in the binder.
  • thermographic film 10 was prepared according to the following procedure.
  • a paper support base was coated with a first layer comprising 0.1g of phthalazinone toner dispersed in 8g of 6% MowitalTM B60H solution in acetone/mek (9/1) (binder), at a wet coating gap of 30 ⁇ m with a Erichsen precision coater.
  • An intermediate layer was coated on the first layer with a coating composition comprising 8g of a 26% silver behenate dispersion in 6% MowitalTM B60H in acetone/mek (1/9) and 0.033 moles of cupric behenate per mole of silver behenate (silver soap), at a wet coating gap of 50 ⁇ m.
  • a third layer was coated on the intermediate layer with a coating composition comprising 0.35g of IrganoxTM 2246 developer dispersed in 8g of a 6% MowitalTM B60H solution in acetone/mek (9/1) (binder), at a wet coating gap of 50 ⁇ m.
  • a protective layer comprising 8g of 6% MowitalTM B60H solution in acetone/mek (9/1) was top-coated at a wet coating gap of 30 ⁇ m.
  • thermographic film 11 was prepared according to the same procedure of sample 10, but the first layer comprises the developer and the third layer comprises the toner.
  • thermographic film 12 was prepared according to the same procedure of sample 10, but the intermediate layer comprises 0.25g of developer, and 0.1g of toner are present in both the first and the third layer.
  • thermographic film 13 was prepared according to the same procedure of sample 10, but the developer is present in both the first and the third layer, dispersed in the binder, and the toner is present in the intermediate layer, together with the silver soap.
  • thermographic film 14 was prepared according to the same procedure of sample 10, but the first layer comprises the silver soap, the intermediate layer comprises the toner dispersed in the binder, at a wet coating gap of 30mm, and the third layer comprises the developer dispersed in the binder.
  • thermographic film 15 was prepared according to the following procedure.
  • a paper support base was coated with a first layer comprising a composition of 8g of a 26% silver behenate dispersion in 6% MowitalTM B60H in acetone/mek (1/9) and 0.033 moles of cupric behenate per mole of silver behenate (silver soap) and 0.35g of dodecyl gallate developer, at a wet coating gap of 50 ⁇ m with a Erichsen precision coater.
  • a second layer was coated on the first layer with a coating composition comprising 0.2g of phthalazinone toner dispersed in 8g of a 6% cellulose biacetate solution in acetone/mek (9/1) (binder), at a wet coating gap of 30 ⁇ m.
  • a protective layer comprising 8g of 6% MowitalTM B60H solution in acetone/mek (9/1) was top-coated at a wet coating gap of 30 ⁇ m.
  • thermographic film 16 was prepared according to the following procedure.
  • a paper support base was coated with a first layer comprising a composition of 8g of a 26% silver behenate dispersion in 6% MowitalTM B60H in acetone/mek (1/9) and 0.033 moles of cupric behenate per mole of silver behenate (silver soap), 0.35g of IrganoxTM 2246 developer, and 0.05g of dodecyl gallate developer, at a wet coating gap of 50 ⁇ m with a Erichsen precision coater.
  • a second layer was coated on the first layer with a coating composition comprising 0.2g of phthalazinone toner dispersed in 8g of a 6% MowitalTM B60H solution in acetone/mek (9/1) (binder), at a wet coating gap of 30 ⁇ m.
  • a protective layer comprising 8g of 6% MowitalTM B60H solution in acetone/mek (9/1) was top-coated at a wet coating gap of 30 ⁇ m.
  • thermographic films 1 to 16 were exposed with a conventional Kyocera KMT-128 thermal print head having 8dots/mm resolution, heating element size of 0.105x0.200mm2, and printing width of 128 mm (1024 dots).
  • the burn profile was designed with a pre-heating of 3060 ⁇ s, followed by additional steps of 70 ON/40 OFF ⁇ s, for a total exposing time of 13620 ⁇ s corresponding to Dmax.
  • the voltage was set at 15.5 Volts.
  • the films were developed by uniform heat exposure at 98°C for 10 sec. The results are summarized in the following Table 1.
  • IrganoxTM 2246 developer is the trade name for a hindered polyphenol having the following formula:
  • the infrared absorbing dye IR-1 is represented by the following formula:
  • the phthalazinone toner is represented by the following formula:
  • thermographic film 17 was prepared according to the following procedure.
  • a paper support base was coated with a layer of thermosensitive composition comprising 8g of a 26% silver behenate dispersion in 6% MowitalTM B60H in acetone/mek (1/9), 0.35g of IrganoxTM 2246 developer, and 0.1g of phthalazinone toner, at a wet coating gap of 50 ⁇ m with a Erichsen precision coater.
  • a protective layer comprising 8g of 6% MowitalTM B60H solution in acetone/mek (9/1) was top-coated at a wet coating gap of 30 ⁇ m.
  • Sample 17a was prepared in the same way of sample 17, but the silver soap layer further comprises 0.033 moles of cupric formate per mole of silver behenate.
  • thermographic film 18 was prepared according to the following procedure.
  • a paper support base was coated with a first layer comprising a composition of 8g of a 26% silver behenate dispersion in 6% MowitalTM B60H in acetone/mek (1/9) (silver soap), at a wet coating gap of 50 ⁇ m with a Erichsen precision coater.
  • a second layer was coated on the first layer with a coating composition comprising 0.35g of IrganoxTM 2246 developer and 0.1g of phthalazinone toner dispersed in 8g of a 6% MowitalTM B60H solution in acetone/mek (9/1) (binder), at a wet coating gap of 50 ⁇ m.
  • a protective layer comprising 8g of 6% MowitalTM B60H solution in acetone/mek (9/1) was top-coated at a wet coating gap of 30 ⁇ m.
  • Sample 18a was prepared in the same way of sample 18, but the silver soap layer comprises 0.033 moles of cupric formate per mole of silver behenate.
  • Thermographic films 19 and 19a were prepared according to the same procedure of samples 18 and 18a, but the order of coating of the first and second layer was inverted.
  • Thermographic films 20 and 20a were prepared according to the same procedure of samples 18 and 18a, but the first layer comprises the developer dispersed in the binder, and the second layer comprises the toner dispersed in the silver soap.
  • Thermographic films 21 and 21a were prepared according to the same procedure of samples 18 and 18a, but the first layer comprises the toner dispersed in the silver soap, and the second layer comprises the developer dispersed in the binder.
  • Thermographic films 22 and 22a were prepared according to the same procedure of samples 18 and 18a, but the first layer composition comprises 0.1g of toner dispersed in the binder and the second layer comprises the silver soap and 0.35g of developer.
  • Thermographic films 23 and 23a were prepared according to the same procedure of samples 18 and 18a, but the first layer comprises the silver soap and the developer, and the second layer comprises the toner dispersed in the binder.
  • thermographic film 24 was prepared according to the following procedure.
  • a paper support base was coated with a first layer comprising 0.35g of IrganoxTM 2246 developer dispersed in 8g of 6% MowitalTM B60H solution in acetone/mek (9/1) (binder), at a wet coating gap of 50 ⁇ m with a Erichsen precision coater.
  • An intermediate layer was coated on the first layer with a coating composition comprising 8g of a 26% silver behenate dispersion in 6% MowitalTM B60H in acetone/mek (1/9) (silver soap), at a wet coating gap of 50 ⁇ m.
  • a third layer was coated on the intermediate layer with a coating composition comprising 0.1 g of phthalazinone toner dispersed in 8g of a 6% MowitalTM B60H solution in acetone/mek (9/1) (binder), at a wet coating gap of 50 ⁇ m.
  • a protective layer comprising 8g of 6% MowitalTM B60H solution in acetone/mek (9/1) was top-coated at a wet coating gap of 30 ⁇ m.
  • Sample 24a was prepared in the same way of sample 24, but the silver soap layer further comprises 0.033 moles of cupric formate per mole of silver behenate.
  • Thermographic films 25 and 25a were prepared according to the same procedure of samples 24 and 24a, but the first layer comprises the toner and the third layer comprises the developer.
  • Thermographic films 26 and 26a were prepared according to the same procedure of samples 24 and 24a, but the first layer comprises the developer dispersed in the binder, the intermediate layer comprises the toner dispersed in the binder and the third layer comprises the silver soap.
  • Thermographic films 27 and 27a were prepared according to the same procedure of samples 24 and 24a, but the first layer comprises the silver soap, the intermediate layer comprises the toner dispersed in the binder and the third layer comprises the developer dispersed in the binder.
  • Thermographic films 28 and 28a were prepared according to the same procedure of samples 24 and 24a, but the first layer comprises the silver soap, the intermediate layer comprises the developer dispersed in the binder and the third layer comprises the toner dispersed in the binder.
  • Thermographic films 29 and 29a were prepared according to the same procedure of samples 24 and 24a, but the first layer comprises the toner dispersed in the binder, the intermediate layer comprises the developer dispersed in the binder and the third layer comprises the silver soap.
  • thermographic films 17 to 29 and 17a to 29a were exposed with a conventional Kyocera KMT-128 thermal print head having 8dots/mm resolution, heating element size of 0.105x0.200mm2, and printing width of 128 mm (1024 dots).
  • the burn profile was designed with a pre-heating of 1275 ⁇ s, followed by 30 steps with 70 ⁇ s ON/70 ⁇ s OFF, 40 steps with 70 ⁇ sON/105 ⁇ sOFF, and 53 steps with 70 ⁇ sON/140 ⁇ sOFF, for a total exposing time of 23605 ⁇ s corresponding to Dmax.
  • the voltage was set at 15.5 Volts. After exposure, the films were developed by uniform heat exposure at 90, 95, 100, and 105°C for 10 sec.
  • cupric formate showed a strong catalytic action in both the formation of the primary image and in its amplification. This allows a reduction of the energy employed to develop the primary image.
  • thermographic film 30 was prepared by coating on white polyester support, with an Erichsen bar coater, a first layer solution comprising 8 g. of 26% a silver behenate dispersion in 6% MowitalTM B60H in acetone/Mek (1/9), comprising also 0.033 moles of cupric behenate per mole of silver behenate, 0.35 g of IrganoxTM 2246 and 0.0025 g. of the IR-1 dye at 50 micron wet gap, followed by a second layer solution coated at 30 micron wet gap comprising 8 g of 6% cellulose diacetate in mek, 0.2 g of phthalazinone toner and 0.075 g of additional IR-1 dye. No protective layer was coated.
  • thermographic film 31 was prepared by coating a first layer solution comprising 8 g. of 26% silver behenate dispersion in 6% cellulose diacetate and including also 0.033 moles of cupric behenate and 1/6 moles of magnesium behenate per mole of silver behenate and 0.0025 g of the IR-1 dye, followed by a second layer solution coated at 30 micron wet gap and comprising 0.2 g of phthalazinone toner and 0.075 g of additional IR-1 dye. No protective layer was coated.
  • the samples 30 and 31 were put on a 10 cm diameter drum laser test bed comprising a laser diode giving 116 mW at 820 nm, on 350 sq. micron spot area and were scanned at increasing drum rotational speed.
  • the film 30 gave a visible yellow primary image at 100 r.p.m (52 cm/s.) with ROD 0.67 and absorption maximum at 440 nm and invisible primary images at 200, 400 and 600 rpm.
  • the film 30 was thermally developed for 5 s at 90°C giving amplification of the yellow primary image obtained at 52 cm/s, which turned to a value of neutral black ROD equal to 1.68, while the invisible primary image band obtained at 200 r.p.m. turned to a value of grey ROD equal to 0.68, the one obtained at 400 r.p.m. turned to a value of grey ROD equal to 0.44 and the last one printed at 600 r.p.m. turned to just a ROD value of 0.12 (over base).
  • the film 31 gave a visible (yellow-brown) latent image too at 100 r.p.m. with ROD equal to 0.32 with absorption maximum at about 445 nm. and invisible ones at higher speed.
  • the exposed film 31 was heat processed for 10 s at 80°C (or 5 s at 85°C) giving neutral black amplified image with ROD equal to 1.2 in the areas exposed at 100 r.p.m. and grey nuance with decreasing ROD values at increasing rotational drum speed, getting amplification threshold at about 600 r.p.m.
  • the film 2 of example 1 was similarly exposed by laser diode way (in addition to the thermal printhead mode) and gave similar yellow primary image (at about 100 rpm) and invisible primary images at increasingly higher rotational speeds, followed by amplification to neutral black and grey images by thermal processing at 97°C for 10 s. It must be stressed the similarity of the sample 2 behavior, when it was imagewise thermally exposed by thermal printhead (as in the described example 1) and when it was exposed by heat converted IR laser beam. In both the cases a partially visible (yellow) primary image is formed and it is amplified to neutral black by uniform thermal processing, indicating that in both the cases the ultimate role of thermal exposure in causing the primary image.
  • FILM 33 EDG-AR-II FILM 34: EDG IR FILM 35: DRC-S FILM 36: EDG-AR-I FILM 37 : RAN FILM 38 : IR PLUS
  • EDG-AR-I FILM 34 EDG IR FILM 35: DRC-S FILM 36: EDG-AR-I FILM 37 : RAN FILM 38 : IR PLUS
  • the obtained primary (or latent) images were not observed in daylight (to prevent the film photoexposure), but were amplified in red safety light in conventional automatic processors conditions and aqueous processing solutions of Graphic Arts and Medical X-ray.

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
  • Electronic Switches (AREA)
EP94115226A 1994-09-27 1994-09-27 Méthode d'enregistrement pour matériau sensible à la chaleur Withdrawn EP0704318A1 (fr)

Priority Applications (2)

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EP94115226A EP0704318A1 (fr) 1994-09-27 1994-09-27 Méthode d'enregistrement pour matériau sensible à la chaleur
JP24941895A JPH08179459A (ja) 1994-09-27 1995-09-27 感熱材料の画像形成方法

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0809141A1 (fr) * 1996-05-22 1997-11-26 Eastman Kodak Company Films photothermographiques et thermographiques à faible taux de formiate pour empêcher du voile
US6340985B1 (en) 1997-12-10 2002-01-22 Fuji Photo Film Co. Ltd. Thermal recording apparatus

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3094619A (en) * 1961-01-03 1963-06-18 Minnesota Mining & Mfg Ultra-violet radiation-desensitizable thermographic copy-sheet and method
US3782941A (en) * 1972-07-18 1974-01-01 Eastman Kodak Co Photothermographic element,composition and process
US5294526A (en) * 1993-02-22 1994-03-15 Eastman Kodak Company Method for the manufacture of a thermally processable imaging element

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2933990B2 (ja) * 1990-06-18 1999-08-16 コニカ株式会社 画像形成方法
JPH05150395A (ja) * 1991-11-28 1993-06-18 Canon Inc 乾式銀塩感光体及びこの感光体を用いた画像形成方法
EP0582144B1 (fr) * 1992-08-03 1997-04-23 Minnesota Mining And Manufacturing Company Matériau d'enregistrement thermosensible adressé par laser
EP0599463A3 (fr) * 1992-11-17 1994-12-07 Minnesota Mining & Mfg Ensemble pour plaque d'impression à grande vitesse pour développement à sec.
GB9305324D0 (en) * 1993-03-16 1993-05-05 Minnesota Mining & Mfg Photothemographic imaging materials and sensitisers therefor
JPH07228051A (ja) * 1994-02-18 1995-08-29 Fuji Photo Film Co Ltd 赤外レーザー記録用感熱記録材料
JPH07295137A (ja) * 1994-04-27 1995-11-10 Canon Inc 画像形成方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3094619A (en) * 1961-01-03 1963-06-18 Minnesota Mining & Mfg Ultra-violet radiation-desensitizable thermographic copy-sheet and method
US3782941A (en) * 1972-07-18 1974-01-01 Eastman Kodak Co Photothermographic element,composition and process
US5294526A (en) * 1993-02-22 1994-03-15 Eastman Kodak Company Method for the manufacture of a thermally processable imaging element

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0809141A1 (fr) * 1996-05-22 1997-11-26 Eastman Kodak Company Films photothermographiques et thermographiques à faible taux de formiate pour empêcher du voile
US6340985B1 (en) 1997-12-10 2002-01-22 Fuji Photo Film Co. Ltd. Thermal recording apparatus

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