EP0385383A2 - Bilderzeugungsverfahren und wärmeentwickelbares lichtempfindliches Farbmaterial zur Verwendung in diesem Verfahren - Google Patents

Bilderzeugungsverfahren und wärmeentwickelbares lichtempfindliches Farbmaterial zur Verwendung in diesem Verfahren Download PDF

Info

Publication number
EP0385383A2
EP0385383A2 EP90103768A EP90103768A EP0385383A2 EP 0385383 A2 EP0385383 A2 EP 0385383A2 EP 90103768 A EP90103768 A EP 90103768A EP 90103768 A EP90103768 A EP 90103768A EP 0385383 A2 EP0385383 A2 EP 0385383A2
Authority
EP
European Patent Office
Prior art keywords
dye
group
image
photosensitive material
general formula
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.)
Withdrawn
Application number
EP90103768A
Other languages
English (en)
French (fr)
Other versions
EP0385383A3 (de
Inventor
Tawara C/O Konica Corporation Komamura
Katsunori C/O Konica Corporation Katoh
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Konica Minolta Inc
Original Assignee
Konica Minolta Inc
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Konica Minolta Inc filed Critical Konica Minolta Inc
Publication of EP0385383A2 publication Critical patent/EP0385383A2/de
Publication of EP0385383A3 publication Critical patent/EP0385383A3/de
Withdrawn legal-status Critical Current

Links

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
    • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
    • G03C8/40—Development by heat ; Photo-thermographic processes
    • G03C8/4013—Development by heat ; Photo-thermographic processes using photothermographic silver salt systems, e.g. dry silver
    • G03C8/4033—Transferable dyes or precursors
    • 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
    • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
    • G03C8/02—Photosensitive materials characterised by the image-forming section
    • G03C8/08—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of organic compounds
    • G03C8/10—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of organic compounds of dyes or their precursors

Definitions

  • the invention relates to a method of forming image by thermal development. More particularly, this invention relates to a method of forming an infrared dye image that can be read with infrared radiation, as well as a heat-­processible or thermally developable photosensitive material suitable for use in that method.
  • ID identification
  • recording materials that carry character information or signal information are often read optically with light longer than 750 nm (which light is hereinafter referred to as "infrared radiation") that is emitted from semiconductor lasers, light-emitting diodes and other light sources.
  • the present inventors have studied as a heat-processible color photosensitive material that contains a dye-providing material that either forms or releases an infrared dye.
  • the heat-processible color photosensitive material still has a need for improvements in various aspects such as the wavelength at which the infrared dye formed absorbs light, its diffusibility and stability under exposure to heat and light.
  • the present invention has been accomplished in order to meet this need.
  • the principal object of the present invention is to provide a method of forming an infrared dye image that has improved stability under exposed to heat and light and that has a wavelength of absorption that enables reading with infrared radiation at even longer wavelengths, as well as a heat-processible color phototsensitive material that is suitable for use in said method.
  • a method which comprises the steps of: providing a heat-processible color phototsensitive material that has at least a light-sensitive silver halide, a reducing agent, a binder and a dye-providing material on a support, which dye-providing material contains either a dye portion represented by the following general formula (1) or a dye portion represented by the following general formula (2) or both; performing imagewise exposure on said phototsensitive material; subsequent to or simultaneously with the imagewise exposure, thermally developing said photosensitive material in close contact with an image-­receiving material; transferring onto said image-receiving material all or part of the diffusible dye containing said dye portion which is formed from said dye-providing material as a function of development; during or after the transfer, chelating part or all of the diffusible dye with a metal to thereby form an image of the chelated dye in said image-receiving material: where X represents
  • the dye portion represented by the general formula (1) or (2) is usually a cyan dye but when it forms a chelate complex with a transition metal ion, the range of its absorption wavelength shifts to the longer side by at least 100 nm and it becomes an infrared dye.
  • a heat-­processible color photosensitive material that contains a dye-providing material having the dye portion represented by the general formula (1) or (2) (which material is hereinafter referred to as the "compound of the present invention") is capable of forming an infrared dye image and/or a cyan dye image.
  • the dye portion represented by the general formula (1) or (2) may be pre-chelated (i.e. preliminarily form a chelate with a metal ion) but from the viewpoint of dye diffusibility, it may more preferably be post-chelated, i.e. from a chelate in the image-receiving layer or in a nearby area such as a portion of the image-receiving material other than the image-receiving layer or the topmost layer of the photosensitive material.
  • X in each of the general formulas (1) and (2) represents the atomic group necessaryy to form an aromatic nitrogenous heterocyclic ring, preferably an atomic group capable of forming a condensed pyridine ring.
  • R1 represents a hydrogen atom, a halogen atom or a monovalent organic group.
  • a preferred halogen atom is a chlorine or fluorine atom.
  • a preferred monovalent organic group is an optionally substituted alkyl group (e.g. methyl or ethyl), an optionally substituted alkoxy group (e.g.
  • R6 and R7 each represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group
  • R8 represents a hydrogen atom, an alkyl group, an aryl group, a cycloalkyl group, a heterocyclic group or an amino group.
  • Each of the groups R1 and R6 to R8 may have a substituent.
  • R1, R6, R7 and R8 When optionally substituted groups such as alkyl, cycloalkyl, aryl and heterocyclic groups are represented by R1, R6, R7 and R8, illustrative substituents that can be used include a halogen atom (e.g.
  • an alkyl group an aryl group, a heterocyclic group, a nitro group, a cyano group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a keto group, a sulfonamido group, a sulfamoyl group, an acylamino group, a carbamoyl group, a sulfonyl group, a sulfinyl group, a hydroxyl group, a carboxyl group, and an amino group which may be primary or secondary.
  • R1 represents a halogen atom or a monovalent organic group
  • a hydrogen atom, a halogen atom or a monovalent organic group is represented by each of R2, R3, R4 and R5 and a preferred halogen atom is chlorine or fluorine.
  • the monovalent organic group may be exemplified by those which are listed in the definition of R1.
  • Preferred examples of the alkyl group represented by each of R6 and R7 are those which have 1 - 4 carbon atoms such as methyl, ethyl, n-propyl and n-butyl. If these alkyl groups are substituted, preferred substituents include an alkoxy group (e.g. methoxy or ethoxy), an alkylsulfoamide group (e.g. methanesulfoamido), a sulfo group, a carboxy group, a sulfamoyl group, a carbamoyl group, etc.
  • an alkoxy group e.g. methoxy or ethoxy
  • an alkylsulfoamide group e.g. methanesulfoamido
  • a sulfo group a carboxy group
  • a sulfamoyl group a carbamoyl group
  • the dye portion represented by the general formula (1) or (2) preferably forms a metal chelate dye either in the image-receiving layer or in an nearby area.
  • the compound (metal source) that is capable of supplying metal ions to form a metal chelate may be organic or inorganic salts of metal ions (e.g. carboxylates or sulfonates) or it may be one of the complexes (e.g. the metal complexes described in "Chelate Chemistry (5)", ed. by Kagehira Ueno, Nankodo).
  • Preferred metal ions are those of divalent transition metals, with divalent nickel, copper, zinc, cobalt, platinum and palladium being particularly preferred.
  • the metal source compound is preferably added in an amount ranging from 0.1 to 10 moles per mole of the compound of the present invention that is incorporated in the photosensitive material.
  • the metal source may be incorporated in the same manner as will be described below in connection with the incorporation of the compound of the present invention. For example, it is dissolvent or dispersed in a low-boiling or high-boiling point solvent and thereafter dissolved or dispersed together with the polymer for forming an image-receiving layer, and the resulting solution or dispersion is applied onto the substrate.
  • the compound of the present invention has a carrier, or a group that allows a dye compound having the dye portion to have different degrees of diffusibility as a function of silver development (i.e. said dye component has a different diffusibility after the development than before the development).
  • This carrier is bonded to at least one of R1, R2, R3, R4, R5 and Y.
  • the carrier to be used in the present invention is described hereinafter.
  • Carriers of the negative type are reducing carriers which are oxidized to release diffusible dyes and may be represented by the following general formulas (3) - (7): where A1 represents the atomic group necessary to form a benzene ring or a naphthalene ring; A2 represents the atomic group necessary to form a condensed benzene ring; the ring formed by A1 or A2 may have substituents, at least one of which is a ballast group; Z1 and Z2 each represents a hydroxyl group, an amino group (inclusive of a substituted amino group) or a group that imparts a hydroxyl group or an amino group (inclusive of a substituted amino group) upon hydrolysis.
  • JP-A-48-33826 the term "JP-A" as used herein means an "unexamined published Japanese patent application"
  • JP-A-­51-113624 JP-A-57-179840
  • JP-A-58-116537 JP-A-59-6043
  • JP-A-59-65839 JP-A-59-165055
  • JP-A-51-104343 JP-A-59-­124329, etc.
  • the dye-providing material may also serve as a reducing agent.
  • Another negative-acting carrier is a coupler residue.
  • the dye portion is substituted at the active site of a coupler, with the coupler residue having at least one ballast group.
  • Specific examples of carriers of this kind are described in the specifications of JP-A-57-122596, JP-A-57-186744, JP-A-­59-159159, JP-A-59-174834, JP-A-59-231540, etc.
  • Still another negative-acting carrier is a coupler that is substituted with a ballast group at the active site, with the dye portion being substituted by a group other than at the active site.
  • Specific examples of the carrier of this type are described in Japanese Patent Application No. 63-257998.
  • positive-acting carriers are described in JP-A-51-63618, JP-A-53-69033, JP-A-54-130927, JP-A-49-111628, JP-A-52-4819, JP-A-53-35533, JP-A-53-­110827, JP-A-54-130927, JP-A-56-164342, and U.S. Patent No. 4,783, 396.
  • the dye portion of the compound of the present invention can be obtained by the methods described in JP-A-­63-227569, Japanese Patent Application No. 62-294600. Briefly stated, it can be obtained by the oxidative coupling reaction between an 8-hydroxyquinolinol derivative and a p-phenylenediamine derivative or p-aminophenol derivative.
  • the compound of the present invention can also be obtained by subjecting the functional group in said dye portion to reaction, say condensation reaction, with the carrier portion either directly or after it is converted to an acid chloride (e.g. sulfonyl chloride).
  • reaction say condensation reaction
  • carrier portion either directly or after it is converted to an acid chloride (e.g. sulfonyl chloride).
  • the compound of the present invention can also be synthesized by first reacting an 8-hydroxyquinolinol derivative with the carrier portion and then subjecting the reaction product to oxidative coupling.
  • the compounds of the present invention described above may be used either independently or as admixtures.
  • the amount of these compounds used is by no means critical and may be determined according to their type, the manner in which they are used (i.e., either singly or in combination) or the number of photographic constituent layers of which the light-sensitive material of the present invention is composed (i.e., a single layer or two or more layers in superposition).
  • the compounds may be used in an amount of 0.005 - 50 g, preferably 0.1 - 10 g, per square meter.
  • the compounds of the present invention may be incorporated in photographic constituent layers in a heat-­processible color photosensitive material by any suitable method. For instance, they are dissolved in low-boiling solvents (e.g., methanol, ethanol and ethyl acetate) and/or high-boiling solvents (e.g., dibutyl phahlate, dioctyl phthalate and tricresyl phosphate) and uniform dispersions are made.
  • the dye compounds are dissolved in alkaline aqueous solutions (e.g., a 10% aqueous solution of sodium hydroxide) and neutralized with acids (e.g., citric acid or nitric acid).
  • the compounds are dispersed in solid form in aqueous solutions of appropriate polymers (e.g., gelatin, polyvinylbutyral and polyvinylpyrrolidone).
  • Light-sensitive silver halides that can be used in the present invention include silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodido, silver iodobromide, etc. These light-sensitive silver halides can be prepared by any of the methods commonly employed in the photographic art.
  • a silver halide emulsion having silver halide grains with a duplex structure i.e., the halide composition of the grain surface differing from that of the interior
  • an example of such duplex grains is core/shell type silver halide grains.
  • the shell of these grains may change in halide composition stepwise or gradually.
  • the silver halide grains used may have a well-­defined crystal habit as in cubes, spheres, octahedra, dodecahedra or tetradecahedra. Alternatively, they may not have any well-defined crystal habit. Illustrative silver halides of this type are shown in JP-A-60-215948.
  • a silver halide emulsion comprising tabular silver halide grains of the type described in JP-A-58-111933, JP-­A-58-111934, JP-A-58-108526 and Research Disclosure No. 22534 may also be used; such grains have two parallel crystal planes each of which has a greater area than any other single crystal of these grains and the aspect ratio (i.e., diameter-to-thickness ratio) of these grains is at least 5:1.
  • the present invention also permits the use of a silver halide emulsion containing internal latent-image forming silver halide grains whose surface is not prefogged.
  • emulsions include: those which comprise silver halide grains having a higher sensitivity in their interior than on the surface, as shown in USP 2,592,250, 3,206,313, 3,327,322, 3,511,622, 3,447,927, 3,761,266, 3,703,584 and 3,746,140; those which comprise silver halide grains having polyvalent metal ions incorporated therein, as shown in USP 3,271,157, 3,447,927 and 3,531,291; those which comprise dopant-containing silver halide grains with their surface being chemically sensitized by a small extent, as shown in USP 3,761,276; those which comprise grains with a multi-layered structure, as shown in JP-A-50-­8254 and JP-A-50-38525; and silver halide emulsions of the type described in JP
  • the silver halide grains in these light-sensitive emulsions may be course or fine; preferred grain sizes are in the order of 0.005 ⁇ m to 1,5 ⁇ m in diameter, with the range of from about 0.01 to about 0.5 ⁇ m being more preferred.
  • a light-sensitive silver salt forming component may be used in the presence of organic silver salts (to be described below) so as to form light-­sensitive silver halides in part of the organic silver salts.
  • These light-sensitive silver halides and light-­sensitive silver salt forming component may be used in combination in a variety of methods, and the amount used in one photographic layer preferably ranges from 0.001 to 50 g, more preferably 0.1 - 10 g, per square meter of support.
  • the light-sensitive silver halide emulsions illustrated above may be chemically sensitized by any of the methods commonly employed in the photographic art.
  • the light-sensitive silver halide emulsion used in the present invention may be spectrally sensitized with known spectral sensitizing dyes to provide sensitivity to blue, green, red or infrared light.
  • spectral sensitizing dyes that can be used in the present invention include cyanine dyes, merocyanine dyes, complex (tri- or tetra-nuclear) cyanine dyes, holopolar cyanine dyes, styryl dyes, hemicyanine dyes and oxonole dyes.
  • sensitizing dyes are incorporated in amounts ranging from 1 x 10 ⁇ 6 to 1 mole, preferably from 1 x 10 ⁇ 5 to 1 x 10 ⁇ 1 mole, per mole of the light-sensitive silver halide or silver halide forming component.
  • the sensitizing dyes may be added at any stage of the preparation of silver halide emulsions; namely, they may be added at any stage such as during the formation of silver halide grains, during the removal of soluble salts, prior to the start of chemical sensitization, during chemical sensitization, or after completion of chemical sensitization.
  • the reducing agent to be used in the heat-processible color photosensitive material of the present (the term "reducing agent" as used herein shall include precursors of the reducing agent) may be selected from among these which are commonly used in the field of heat-processible photosensitive materials.
  • Reducing agents that can be used in the present invention are described in, for example, USP 3,531,286, 3,761,270, 3,764,328, Research Disclosure Nos. 12146, 15108 and 15127, JP-A-56-27132, USP 3,342,599, 3,719,492, JP-A-­53-135628 and JP-A-57-79035, and they include: p-­phenylenediamino and p-aminophenolic developing agents, phosphoroamidophenolic and sulfonamidoaniline based developing agents, hydrazone based color developing agents, and precursors thereof, as well as phenols, sulfonamidophenols, polyhydroxybenzenes, naphthols, hydroxybinaphthyls, methylenebisnaphthols, methylenebisphenols, ascorbic acids, 3-pyrazolidones and pyrazolones.
  • Dye-providing materials may themselves serve as reducing agents.
  • Particularly preferred reducing agents are N-(p-N,N-­dialkylamino) phenylsulfamic acid salts as described in JP-­A-56-146133 and JP-A-62-727141.
  • the reducing agents described above may be used either independently or as admixtures.
  • the amount in which the reducing agents are used in the heat-processible color photographic material of the present invention depend upon many factors such as the type of light-sensitive silver halide used, the type of organic silver salt, and the type of other additives used.
  • the reducing agents are used in amounts ranging from 0.01 to 1,500 moles, more preferably from 0.1 to 200 moles, per mole of the light-sensitive silver halide.
  • Illustrative binders that can be employed in the heat-­processible color photosensitive material of the present invention include: synthetic high-molecular compounds such as polyvinylbutyral, polyvinyl acetate, ethyl collulose, polymethyl methacrylate, cellulose acetate butyrate, polyvinyl alcohol and polyvinylpyrrolidone; synthetic or natural high-molecular compounds such as gelatin, gelatin derivatives (e.g., phthalated gelatin), cellulose derivatives, proteins, starches, and gum arabic. These high-molecular compounds may be used either singly or in combination.
  • synthetic high-molecular compounds such as polyvinylbutyral, polyvinyl acetate, ethyl collulose, polymethyl methacrylate, cellulose acetate butyrate, polyvinyl alcohol and polyvinylpyrrolidone
  • synthetic or natural high-molecular compounds such as gelatin, gelatin derivatives (e.g., phthalated gelatin
  • gelatin or its derivatives in combination with hydrophilic polymers such as polyvinylpyrrolidone and polyvinyl alcohol.
  • hydrophilic polymers such as polyvinylpyrrolidone and polyvinyl alcohol.
  • a more preferred binder is a mixture of gelatin and polyvinylpyrrolidone as disclosed in JP-A-59-229556.
  • the binders are generally used in amounts ranging from 0.05 to 50 g, preferably from 0.2 to 20 g, per square meter of a support.
  • the binders are preferably used in amounts of 0.1 - 10 g, more preferably 0.2 - 5 g, per gram of the dye-­providing material.
  • the color light-sensitive material of the present invention may contain not only the compound of the present invention but also other dye-providing materials.
  • optionally used dye-providing materials include couplers capable of forming non-diffusible dyes as described in JP-A-62-44737, JP-A-62-129852 and JP-A-62-­169158, leuco dyes as described in USP 475,441, and azo dyes for use in a heat development dye bleaching method as described in USP 4,235,957. More preferably, diffusion-­type dye-providing materials which are capable of forming or releasing diffusible dyes are used, and it is particularly preferred to use compounds that form diffusible dyes by coupling reaction.
  • Any diffusion-type dye-providing materials can be used as long as they are capable of forming or releasing diffusible dyes as a function of the reduction reaction of light-sensitive silver halides and/or optionally used organic silver salts, and depending on the type of reaction involved, such dye-providing materials are classified as negative-acting dye-providing materials and positive-acting dye-providing materials.
  • Illustrative negative-acting dye-providing materials are reducing dye-releasing compounds of the types described in USP 4,463,079, 4,439,513, JP-A-59-60434, JP-A-59-65839, JP-A-59-71046, JP-A-59-87450, JP-A-59-88730, JP-A-59-­123837, JP-A-59-124329, JP-A-59-165054, JP-A-59-164055, etc.
  • negative-acting dye-providing materials are coupling dye-releasing compounds of the types described in USP 4,474,867, JP-A-59-12431, JP-A-59-48765, JP-A-59-­174834, JP-A-59-776642, JP-A-59-159159, JP-A-59-231040, etc.
  • Coupling dye-forming compounds which are particularly preferred negative-acting dye-providing materials are represented by the following general formula (A): CO ( ⁇ J ) ⁇ ( ⁇ B ) (A) where Cp represents an organic group (coupler residue) capable of entering into reaction (coupling reaction) with the oxidation product of a reducing agent to form a diffusible dye; J represents a divalent linkage group bound to the active site reacting with the oxidation product of a reducing agent; and B is a ballast group.
  • the ballast group renders the dye-providing material to be substantially non-diffusible during heat development and it may exhibit this action on account of either its molecular nature (as in a sulfo group) or its size (as in a group having a large number of carbon atoms).
  • the coupler residue represented by Cp preferably has a molecular weight of no higher than 700, more preferably no higher than 500.
  • the ballast group preferably has at least 8 carbon atoms, more preferably at least 12 carbon atoms, and a group comprising a polymer chain is particularly preferred.
  • a preferred example of the coupling dye-forming compound having a polymer-chain group is such that said group is composed of a polymer chain having recurring units derived from a monomer represented by the following general formula (B): Co ( ⁇ J ) ⁇ ( ⁇ Y ) ⁇ l ( ⁇ Z ) ⁇ ( ⁇ L ) (B) where Cp and J are the same as defined in the general formula (A); Y is an alkylene, arylene or aralkylene group; l is 0 or 1; Z is a divalent organic group; and L is an ethylenically unsaturated group or a group having an ethylenically unsaturated group.
  • B general formula
  • coupling dye-forming compounds represented by the general formulas (A) and (B) include those which are described in JP-A-59-124339, JP-A-­50-181345, JP-A-60-2950, JP-A-61-57943, JP-A-61-59336, USP 4,631,251, 4,650,748, 4,656,124, etc.
  • Particularly preferred are polymer-type dye-providing materials as described in USP 4,656,124, 4,631,251 and 4,650,748.
  • Exemplary positive-acting dye-providing materials include compounds of the types described in JP-A-59-55430, JP-A-59-165054, JP-A-154445, JP-A-59-766954, JP-A-59-­116655, JP-A-59-124327, JP-A-59-152440, etc.
  • These dye-providing materials may be used either on their own or as admixtures.
  • the amounts of their use is by no means critical and may be determined according to their type, the manner in which they are used (i.e. either singly or in combination) or the number of photographic constituent layers of which the light-sensitive material of the present invention is composed (i.e., a single layer or two or more layers in superposition).
  • these dye-providing materials may be used in an amount of 0.005 - 50 g, preferably 0.1 - 10 g, per square meter.
  • the dye-providing materials to be used in the present invention may be incorporated in photographic constituent layers in a heat-processible color photosensitive material by any suitable method. For instance, they are dissolved in a low-boiling solvent (e.g. methanol, ethanol or ethyl acetate) and/or a high-boiling solvent (e.g. dibutyl phthalate, dioctyl phthalate or tricresyl phosphate) and uniform dispersions are made.
  • the dye-­providing materials are dissolved in alkaline aqueous solutions (e.g. a 10% aqueous solution of sodium hydroxide) and neutralized with acids (e.g. citric acid or nitric acid).
  • the dye-providing materials are dispersed in solid form in aqueous solutions of appropriate polymers (e.g., gelatin, polyvinylbutyral and polyvinyl­pyrrolidone).
  • a variety of organic silver salts may optionally be employed in the heat-processible color photosensitive material of the present invention in order to increase its sensitivity or improve its developability.
  • Illustrative organic silver salts that may be employed in the heat-processible color photosensitive material of the present invention include: silver salts of long-chain aliphatic carboxylic acids and silver salts of carboxylic acids having a hetero ring, such as silver behenate and silver ⁇ -(1-phenyltetrazolethio)acetate (see JP-A-53-4921, JP-A-49-52626, JP-A-52-141222, JP-A-53-36224, JP-A-53-­37626, JP-A-53-37610, USP 3,330,633, 3,794,496 and 4,105,451); and silver salts of an imino group as described in Japanese Patent Publication Nos. JP-A-44-26582, 45-­ 12700, 45-18416, 45-22185, JO-A-52-137321; JP-A-58-118638, JP-A-58-118639, and USP 4,123,274.
  • silver salts of an imino group are preferred.
  • silver salts of benzotriazole derivatives such as 5-methylbenzotriazole or derivatives thereof, sulfobenzotriazole or derivatives thereof and N-­alkylsulfamoylbenzotriazole or derivatives thereof.
  • organic silver salts may be used either singly or as admixtures in the present invention.
  • Silver salts prepared in suitable binders may be immediately used without being isolated.
  • isolated silver salts may be dispersed in binders by suitable means before they are used. Methods of obtaining dispersions are illustrated by, but are in no way limited, to a ball mill, a sand mill a vibration mill, etc.
  • the organic silver salts are preferably used in amounts ranging from 0.01 to 500 moles, more preferably from 0.1 to 100 moles, most preferably from 0.3 to 30 moles, per mole of the light-sensitive silver halide.
  • thermal solvents are preferably incorporated in the light-sensitive material and/or the image-receiving member.
  • Thermal solvents usable in the present invention are compounds that are liquid during thermal development and that promote thermal development and/or heat transfer. Examples of such compounds are the polar organic compounds that are described in USP 3,347,675, 3,667,959, Research Disclosure No.
  • JP-A-59-229556 JP-A-59-68730, JP-A-59-84236, JP-A-60-191251, JP-A-60-232547, JP-A-60-­14241, JP-A-61-52643, JP-A-62-78554, JP-A-62-42153, JP-A-­62-44737, USP 3,438,776, 3,666,477, 3,667,959, JP-A-51-­19525, JP-A-53-24829, JP-A-53-60223, JP-A-58-118640, and JP-A-58-198038.
  • Particularly useful compounds are: urea derivatives (e.g., dimethylurea, diethylurea and phenylurea), amide derivatives (e.g., acetamide, benzamide and p-toluamide), sulfonamide derivatives (e.g., benzenesulfonamide and ⁇ -toluenesulfonamide), and polyhydric alcohols (e.g., 1,6-hexanediol, 1,2-­cyclohexanediol and pentaerythritol, and polyethylene glycol.
  • urea derivatives e.g., dimethylurea, diethylurea and phenylurea
  • amide derivatives e.g., acetamide, benzamide and p-toluamide
  • sulfonamide derivatives e.g., benzenesulfonamide and ⁇ -toluenesulfonamide
  • thermal solvents water-insoluble solid thermal solvents may be used with particular advantage.
  • Thermal solvents may be incorporated in various layers such as light-sensitive silver halide emulsion layers, intermediate layers, protective layers, and image-receiving layers in an image-receiving member so that the results desired in respective cases can be obtained.
  • Thermal solvents are usually incorporated in amounts ranging from 10 to 500 wt%, preferably from 30 to 200 wt%, of the binder.
  • Organic silver salts and thermal solvents may be dispersed in the same dispersion.
  • the binder, dispersion medium and disperser to be employed in this case may be the same as those used in preparing dispersions of the individual components.
  • the heat-­processible color photosensitive material of the present invention may incorporate various other additives such as a development accelerator, an antifoggant and a base precursor.
  • a development accelerator such as JP-A-59-177550, JP-A-59-111636 and JP-A-59-124333, the development accelerator releasing compounds described in JP-A-61-159642 and Japanese Patent Application No. 62-203908, and the metallic ion having an electronegativity of 4 or more as described in Japanese Patent Application No. 63-104645.
  • Illustrative antifoggants include: the higher aliphatic compound described in USP 3,645,739; the mercuric salt described in Japanese Patent Publication No.
  • Other preferred antifoggants include the restrainer having a hydroxyl group that is described in JP-A-62-78554, the polymeric restrainer described in JP-A-62-121452, and the restrainer compound having a ballast group that is described in JP-A-62-123456.
  • the colorless coupler described in Japanese Patent Application No. 62-320599 is another anti-foggant that is preferably used.
  • Illustrative base precursors include compounds that undergo decarboxylation upon heating to release a basic substance (e.g., guanidium trichloroacetate) and compounds that are decomposed by reactions such as intramolecular nucleophilic substitution reaction to release amines.
  • a basic substance e.g., guanidium trichloroacetate
  • Examples of such base releasers are described in many prior patents such as JP-A-56-130745, JP-A-56-132332, BP 2,079,480, USP 4,060,420, JP-A-59-157637; JP-A-59-166943, JP-A-59-180537, JP-A-59-174830, JP-A-59-195237, JP-A-62-­108249, and JP-A-62-174745.
  • additives may also be incorporated in the heat-­processible color photosensitive material of the present invention.
  • Illustrative additives include anti-halation dyes, brighteners, hardeners, antistats, plasticizers, extenders, matting agents, surface-active agents and anti-­fading agents. Specific examples are given in Research Disclosure, Vol. 170, No. 17029, June 1978, and JP-A-62-­135825.
  • additives may be incorporated not only in the light-sensitive layers but also in non-light-­sensitive layers such as an intermediate layer, a protective layer and a backing layer.
  • the heat-processible color photosensitive material of the present invention comprises (a) a light-sensitive silver halide, (b) a reducing agent, (c) a binder and (d) a dye-providing material. If necessary, (e) an organic silver salt is preferably contained. Basically, these components may be contained in one thermally developable light-sensitive layer but they are not necessarily incorporated in a single photographic constituent layer and may be incorporated in two thermally developable light-­sensitive layers, with (a), (b), (c) and (e) being contained in one thermally developable light-sensitive layer and the dye-providing material (d) contained in the adjacent other layer. If necessary, these components may be incorporated in more than two constituent layers in such a way that they are held mutually reactive.
  • the thermally developable light-sensitive layer may be divided into two or more layers including a highly sensitive layer and a less sensitive layer, or a high-density layer and a low-density layer.
  • the thermally developable light-sensitive material of the present invention has one or more thermally developable light-sensitive layers on a support.
  • a full-color light-­sensitive material generally has three thermally developable light-sensitive layers having different color sensitivities, each light-sensitive layer forming or releasing a dye of different color as a result of thermal development.
  • a blue-sensitive layer is usually combined with a yellow dye, a green-sensitive layer with a magenta dye, and a red-sensitive layer with a cyan dye. Other combinations may of course be employed. Combination with a near infrared sensitive layer is also possible.
  • a support is coated with a red-sensitive, a green-sensitive and a blue-­sensitive layer, or in the reverse order (i.e., a blue-­sensitive, a green-sensitive and a red-sensitive layer), or a support may be coated with a green-sensitive, a red-­sensitive and a blue-sensitive layer.
  • the heat-processible color photosensitive material of the present invention may incorporate non-light-sensitive layers such as a subbing layer, an intermediate layer, a protective layer, a filter layer, a backing layer and a release layer.
  • non-light-sensitive layers such as a subbing layer, an intermediate layer, a protective layer, a filter layer, a backing layer and a release layer.
  • the thermally developable light-sensitive layers and these non-light-­sensitive layers may be applied to a support by coating techniques that are similar to those commonly employed to coat and prepare ordinary silver halide light-sensitive materials.
  • the heat-processible color photosensitive material of the present invention can be produced by forming photographic constituent layers on a support.
  • Usable support include: synthetic plastic films such as a polyethylene film, a cellulose acetate film, a polyethylene terephthalate film, and a polyvinyl chloride film; paper supports such as a photographic raw paper, printing paper, art paper, cast-coated paper, baryta paper and resin-coated paper; and supports prepared by coating these materials with electron-beam curable resin compositions, followed by curing of the same.
  • the heat-processible color photosensitive material of the present invention is developed after imagewise exposure and this can usually be done merely by heating the material at a temperature in the range of 80 - 200°C, preferably 100 - 170°C, for a period of from 1 - 180 seconds, preferably 1.5 - 120 seconds.
  • a diffusible dye may be transferred onto an image-receiving layer simultaneously with thermal development by bringing the image-receiving layer in the image-receiving member into intimate contact with the light-sensitive surface of the light-sensitive material; alternatively, the light-sensitive material brought into intimate contact with the image-receiving member after thermal development may be subsequently heated.
  • water is supplied before the two members are brought into intimate contact with each other and the assembly is subsequently heated if desired.
  • the light-­sensitive material may be preliminarily heated in the temperature range of 70 - 180°C prior to exposure.
  • they may be separately heated at a temperature of 80 - 250°c just prior to thermal development and transfer, as described in JP-A-­60-143338 and JP-A-61-162041.
  • the heat-processible color photosensitive material of the present invention permits the use of various heating techniques.
  • the light-sensitive material may be brought into contact with a heated block or plate, or with heated rollers or a hot drum. Alternatively, the material may be passed through a hot atmosphere. High-frequency heating is also applicable.
  • an electroconductive layer containing a conductive material such as carbon black is provided either on the back side of the light-sensitive material of the present invention or on the surface of an image-receiving member for heat-transfer and an electric current is applied to generate the Joule heat as heating energy.
  • the heating pattern is in no way limited; preheating may be followed by another cycle of heating; heating may be performed for a short period at high temperatures or for a long period at low temperatures; the temperature may be elevated and lowered continuously; repeated cycles of heating may be employed; the heating may be discontinuous rather than continuous. In any event, a simple heating pattern is preferred. If desired, exposure and heating may proceed simultaneously.
  • an image-receiving member is used if the heat-processible color photosensitive material of the present invention is of a transfer type. Any image-­receiving member may effectively be used in the present invention if the image-receiving layer employed has a capability for accepting the dye released or formed in the thermally developable light-sensitive layer as a result of thermal development.
  • a preferred example is a polymer containing a tertiary amine or a quaternary ammonium salt, as described in USP 3,709,690.
  • Typical image-receiving layers suitable for use in diffusion transfer can be prepared by coating a support with a mixture in which a polymer containing an ammonium salt or a tertiary amine is combined with gelatin or polyvinyl alcohol.
  • Another useful dye-receiving layer may be formed of a heat-resistant organic high-molecular substance having a glass transition point of 40 - 250°c as described in JP-A-57-207250.
  • These polymers may be carried as image-receiving layers on a support; alternatively, they may be used as supports on their own.
  • Synthetic polymers having glass transition points of 40°C and above as described in "Polymer Handbook", 2nd ed., edited by J. Brandrup and E. H. Immergut, John Wiley & Sons are also useful polymers.
  • Useful molecular weights of these high-molecular substances are generally in the range of 2,000 - 200,000. These high-molecular substances may be used either independently or as blends. Two or more monomers may be employed to make copolymers.
  • Particularly preferred image-receiving layers include the polyvinyl chloride layer described in JP-A-59-223425 and the layer described in JP-A-60-19138 that comprises a polycarbonate and a plasticizer.
  • the polymers described above may be used as supports that also serve as image-receiving layers to form image-­receiving members.
  • the support may be formed of a single layer or two ore more layers.
  • Supports for image-receiving members may be transparent or non-transparent.
  • Illustrative supports include: films of polymers such as polyethylene terephthalate, polycarbonate, polystyrene, polyvinyl chloride, polyethylene and polypropylene; supports having pigments such as titanium oxide, barium sulfate, calcium carbonate and talc incorporated in these plastic films; baryta paper; resin-coated (RC) paper having paper laminated with pigment-loaded thermoplastic resins; fabrics; glass; metals such as alminum; supports prepared by coating these materials with pigment-loaded electron beam curable resin compositions, followed by curing of the latter; and supports having pigment-loaded coating layers on these materials.
  • RC resin-coated
  • supports prepared by coating these materials with pigment-loaded electron beam curable resin compositions, followed by curing of the latter and supports having pigment-loaded coating layers on these materials.
  • Also usable as a support is the cast-­coated paper described in JP-A-62-283333.
  • These supports can immediately be used as image-receiving layers since the resin layer itself serves as an image-receiving layer.
  • the heat-processible color photosensitive material of the present invention may be of a "monosheet" type that has both a light-sensitive layer and an image-receiving layer formed on the same support, as described in Research Disclosure (RD) No. 15108 and JP-A-57-198458, JP-A-57-­207250 and JP-A-61-80148.
  • the heat-processible color photosensitive material of the present invention and/or the image-receiving member are preferably provided which a protective layer.
  • the protective layer may contain a variety of additives that are commonly employed in the photographic industry. Suitable additives include matting agents, colloidal silica, slip agents, organofluoro compounds (in particular, fluorine-based surface active agents), antistats, uv absorbers, high-boiling organic solvents, antioxidants, hydroquinone derivatives, polymer latices, surface-active agents (including high-molecular surface-­active agents), hardeners (including high-molecular hardeners), particulate organic silver salts, non-light-­sensitive silver halide grains, antifoggants, development accelerators, etc.
  • matting agents colloidal silica, slip agents, organofluoro compounds (in particular, fluorine-based surface active agents), antistats, uv absorbers, high-boiling organic solvents, antioxidants, hydroquinone derivatives, polymer latices, surface-active agents (including high-molecular surface-­active agents), hardeners (including high-molecular
  • a multi-layered photosensitive material (sample No. 1) having the composition shown in Table 1 was prepared.
  • the high-molecular weight dye-providing materials, reducing agent (CDP), thermal solvent (A), restrainer (A) and scavenger (A) that are mentioned in Table 1 had the following structures.
  • sample No. 2 Another photosensitive material (sample No. 2) was prepared by repeating the procedure described above except that the composition of the sixth layer (blue-sensitive layer) was changed as shown below.
  • Composition of the sixth layer in sample No. 2 Benzotriazole 2.5 g Reducing agent (CDP) 1.6 g Dibutyl phthalate 0.4 g High-molecular weight dye-providing material (1) 0.8 g Blue-sensitive silver halide emulsion 076 g Ag Gelatin 4.8 g Polyvinylpyrrolidone (K-30) 0.6 g Thermal solvent (A) 6.0 g
  • Compound (17) of the present invention 1.0 g Restrainer (A) 0.025 g Scavenger (A) 0.16 g
  • sample Nos. 3 and 4 were prepared like sample No. 2 except that compound (17) of the present invention was replaced by compound (25) of the present invention and comparative compound (A) (see below), respectively:
  • Each of the photosensitive materials (sample Nos. 1 - 4) was exposed to white, blue, green and red light through a step wedge and thermally developed at 145°C for 90 sec in superposition on an image-receiver member No. 1 or 2 having the composition shown below.
  • a black, a cyan, a magenta or a yellow image of high density and low fog was transferred onto the image-receiving member No. 2.
  • the black image was subjected to reflection density measurements with infrared light (850 nm) and the maximum density (Dmax) and minimum density (fog, Dmin) were as shown in Table 2.
  • a multi-layered photosensitive material (sample No. 5) having the composition shown in Table 3 was prepared.
  • Another photosensitive material (sample No. 6) was prepared by repeating the same procedure except that compound (2) of the present invention was replaced by compound (21) of the present invention.
  • each of the samples was exposed to green, red and infrared light through a step wedge and wire-bar coated with water on the emulsion-coated side. Thereafter, the samples of photosensitive material were thermally developed at 130°C for 30 sec in superposition on an image-receiving member No. 3, 4 or 5 having the composition shown below. In response to the exposing light used, a cyan, a magenta and a yellow image was transferred onto the image-receiving members.
  • the cyan image was subjected to reflection density measurements with infrared light (850 nm) and the maximum density (Dmax) and minimum density (fog, Dmin) were as shown in Table 4.
  • Photographic baryta paper coated with a lime-processed gelatin layer (deposit, 2.3 g/m2), which in turn was coated with a dye adherent layer having the composition shown below:
  • the images obtained on the image-receiving member (Nos. 3, 4 and 5) were exposed for 24 h under a xenon lamp (6,000 W) to give a light intensity of 60,000 lux on the surface of each image-receiving layer.
  • Maximum density was measured both before and after the exposure (Do before exposure and D after exposure) and the percentage of residual image [ ⁇ D/Do) ⁇ 100 (%)] was calculated to evaluate the lightfastness of each image.
  • the images were also left in a hot and humid atmosphere (60°C ⁇ 70% r.h.) for 7 days and their heat resistance was evaluated by calculating the percentage of residual image from the maximum density as measured both before and after the storage. Values higher than 90% would be acceptable for practical purposes with respect to both lightfastness and heat resistance.
  • An additional photosensitive material was prepared by repeating the procedure for the preparation of sample No. 5 except that nickel stearate (deposit, 1.0 g/m2) was incorporated in the protective layer. With this photosensitive material, a satisfactory image was formed of the infrared dye even when it was used in combination with the image-receiving member No. 3. The Dmax of this image was 1.12.
  • a multi-layered photosensitive material (sample No. 7) having the composition shown in Table 5 was prepared.
  • Another photosensitive material (sample No. 8) was prepared by repeating the same procedure except that compound (17) of the present invention was replaced by compound (24) of the present invention.
  • Example Nos. 7 and 8 Each of the photosensitive materials (sample Nos. 7 and 8) was exposed as in Example 2 and subsequently processed as in Example 1 in superposition on the image-­receiving member No. 2. In response to the exposing light, a cyan, a magenta and a yellow image of high density and low fog were transferred onto the image-receiving member No. 2. Further, an image was also formed of the infrared dye in the cyan image forming area.
  • the present invention is capable of producing an infrared dye image that is highly stable under exposure to heat and light and that has an absorption wavelength that allows for reading with infrared radiation.

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
EP19900103768 1989-02-27 1990-02-27 Bilderzeugungsverfahren und wärmeentwickelbares lichtempfindliches Farbmaterial zur Verwendung in diesem Verfahren Withdrawn EP0385383A3 (de)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP4562989 1989-02-27
JP45629/89 1989-02-27
JP209821/89 1989-08-14
JP20982189A JPH02289853A (ja) 1989-02-27 1989-08-14 画像形成方法及び該方法に用いる熱現像カラー感光材料

Publications (2)

Publication Number Publication Date
EP0385383A2 true EP0385383A2 (de) 1990-09-05
EP0385383A3 EP0385383A3 (de) 1992-03-18

Family

ID=26385655

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19900103768 Withdrawn EP0385383A3 (de) 1989-02-27 1990-02-27 Bilderzeugungsverfahren und wärmeentwickelbares lichtempfindliches Farbmaterial zur Verwendung in diesem Verfahren

Country Status (2)

Country Link
EP (1) EP0385383A3 (de)
JP (1) JPH02289853A (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994014620A1 (en) * 1992-12-22 1994-07-07 Polaroid Corporation Thermographic image-recording material
EP0573048A3 (de) * 1992-06-05 1995-02-01 Konishiroku Photo Ind Verfahren zur Herstellung eines Bildes.

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3998637A (en) * 1974-07-10 1976-12-21 Eastman Kodak Company Process for producing positive color diffusion transfer images using redox dye releasers
JPS59152440A (ja) * 1983-02-18 1984-08-31 Fuji Photo Film Co Ltd 画像形成方法
JPH0250148A (ja) * 1988-05-16 1990-02-20 Konica Corp 熱現像カラー感光材料

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0573048A3 (de) * 1992-06-05 1995-02-01 Konishiroku Photo Ind Verfahren zur Herstellung eines Bildes.
WO1994014620A1 (en) * 1992-12-22 1994-07-07 Polaroid Corporation Thermographic image-recording material
US5436108A (en) * 1992-12-22 1995-07-25 Polaroid Corporation Thermographic image-recording materials

Also Published As

Publication number Publication date
EP0385383A3 (de) 1992-03-18
JPH02289853A (ja) 1990-11-29

Similar Documents

Publication Publication Date Title
EP0330478A2 (de) Durch Wärme entwickelbares photoempfindliches Material
CA1243536A (en) Dry image-forming process
US4847188A (en) Thermally developable light-sensitive material
US4948698A (en) Heat-processible color photographic material
JPH06507259A (ja) 像記録材料
EP0385383A2 (de) Bilderzeugungsverfahren und wärmeentwickelbares lichtempfindliches Farbmaterial zur Verwendung in diesem Verfahren
EP0123904B1 (de) Wärmeentwickelbares photographisches Material
EP0269291B1 (de) Wärmeentwickelbares farbphotographisches Material und Verfahren zur Bildherstellung
CA1256733A (en) Heat-developable light-sensitive material
JPH0362255B2 (de)
EP0342553A2 (de) Wärmeentwickelbares farbfotoempfindliches Material
JPS6261940B2 (de)
JPH01161239A (ja) 熱現像カラー感光材料
JPH0373949A (ja) 熱現像カラー感光材料及び画像形成方法
JPH02271353A (ja) 熱現像カラー感光材料
US5093229A (en) Heat developable light-sensitive material containing an amidine based precursor
JP2630588B2 (ja) 色濁りの改良された熱現像感光材料
JPH02275942A (ja) 熱現像カラー感光材料
JP2597908B2 (ja) ハロゲン化銀カラー写真感光材料
JPH04296750A (ja) 画像形成方法及び該方法に用いる熱現像感光材料
JPH02289854A (ja) 熱現像カラー感光材料
JPS63243939A (ja) 高濃度でかつ低カブリの熱現像感光材料
JPH0682206B2 (ja) 拡散転写型熱現像カラ−感光材料用受像要素
JPH083620B2 (ja) 新規な青光吸収染料を含有する層を有する熱現像カラ−感光材料
JPH02864A (ja) 画像保存性及びカブリの改良された熱現像感光材料

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): DE GB

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): DE GB

17P Request for examination filed

Effective date: 19920908

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN

18W Application withdrawn

Withdrawal date: 19931214