USH456H - Thermodevelopable silver halide photographic material and process for producing images therewith - Google Patents

Thermodevelopable silver halide photographic material and process for producing images therewith Download PDF

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Publication number
USH456H
USH456H US06/697,551 US69755185A USH456H US H456 H USH456 H US H456H US 69755185 A US69755185 A US 69755185A US H456 H USH456 H US H456H
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US
United States
Prior art keywords
dye
thermodevelopable
photographic material
silver halide
donating substance
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Abandoned
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US06/697,551
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English (en)
Inventor
Hiroshi Hara
Noboru Ohta
Tsuneo Suzuki
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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Assigned to FUJI PHOTO FILM CO., LTD., NO. 210, NAKANUMA, MINAMI ASHIGARA-SHI, KANAGAWA, JAPAN reassignment FUJI PHOTO FILM CO., LTD., NO. 210, NAKANUMA, MINAMI ASHIGARA-SHI, KANAGAWA, JAPAN ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: HARA, HIROSHI, OHTA, NOBORU, SUZUKI, TSUNEO
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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
    • 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

Definitions

  • thermodevelopable photographic material adapted for use in a process which comprises forming a dye image by heating the material in a substantially water-free condition and transferring it to a dye fixing layer to form an image which is substantially black at high density, gray at low density, and can replace silver images.
  • Photographic processes involving the use of silver halides have been widely used heretofore because of their superior photographic properties, such as sensitivity, tone adjustment etc., in contrast to other photographic processes such as electrophotography or diazo photography.
  • thermodevelopable materials are known in the art, and thermodevelopable materials and processes therefore are described, for example, in Fundamentals of Photographic Engineering (a Japanese-language publication published by Corona Co. in 1979), pages 553-555; Image Information (published April 1978), page 40; Nebletts Handbook of Photography and Reprography, 7th Ed., 1977 published by Van Nostrand Reinhold Company, pages 32-33, U.S. Pat. Nos. 3,152,904, 3,301,678, 3,392,020 and 3,457,075, British Pat. Nos. 1,131,108 and 1,167,777, and Research Disclosure, June 1978, pages 9-15 (RD No. 17029).
  • black-and-white images have been largely replaced by color images because of the large quantities of information and the ease of expression, but in many fields, for example in medical therapy, black-and-white images are still preferred.
  • One object of this invention is to provide a new photographic material which is able to provide a substantially black or gray dye image by transferring a mobile dye released by heating in a substantially water-free condition to a dye fixing layer.
  • Another object of this invention is to provide a photographic material which is able to provide images wherein silver is not substantially contained and the unused silver halide or organic silver salt oxidizing agents are fixed.
  • Still another object of this invention is to provide a process for forming black or gray images having excellent storage stability by a dry processing treatment.
  • a further object of this invention is to provide a process for obtaining pleasing black to gray images, hue or tone of which is not changed depending on a light level of an object by a simple procedure.
  • the present invention achieves these objects and provides a solution to the aforesaid problems of known photographic materials by forming a substantially black or gray dye image in the process of forming colored images by heating in a substantially water-free condition.
  • L*a*b* color indicating system is described in Commission International de I'Eclarrage Colorimetry, 2nd Ed. Official Recommendations of the International Commission on Illumination, CIE Publication No. 15.2 (TC-1.3) 1982.
  • a* and b* can be measured by using a color analyzer, for example, Color Analyzer Type 670, made by Hitachi Limited.
  • the invention does not depend on L* (light level). In other words, the effect of this invention does not depend on L*.
  • the mobile dye which forms an image may be one dye or a mixture of two or more dyes.
  • heating after imagewise exposure provides a silver image and a mobile dye corresponding to the silver image.
  • a dye image can be obtained which does not contain silver, silver halides or other undesired compounds.
  • Formation or releasing of a mobile dye in response to, or inverse response to, the reduction of a silver halide to silver by heating denotes the following four reactions which occur following the formation of a development nucleus in silver halide by exposure and the oxidation-reduction reaction of the silver halide with a reducing agent or a reducing dye donating substance in the case of a negative silver halide emulsion, for example.
  • the reducing agent is oxidized, and the oxidized product reacts with the compound capable of forming or releasing the mobile dye to form or release the mobile dye.
  • the reducing agent is oxidized, and the remaining reducing agent and the dye donating substance capable of releasing a mobile dye by heating undergo oxidation-reduction reaction to form a reduction product of the dye donating substance which does not release a mobile dye.
  • the unreduced dye donating substance releases a mobile dye by heating.
  • the reducing dye donating substance is oxidized to a mobile dye.
  • the reducing dye donating substance capable of releasing a mobile dye by heating is oxidized to form an oxidation product which does not release a mobile dye, and the unoxidized dye donating material releases a mobile dye by heating.
  • the dye donating substance useful in this invention is represented by the following formula
  • D represents a dye moiety or its precursor moiety
  • Y represents a substrate having functionality such that the diffusibility of the dye donating substance represented by formula (I) changes by the oxidation-reduction reaction induced in the process of thermal development.
  • That the "diffusibility changes” means that (1) the compound represented by formula (I) which is inherently non-diffusible is rendered diffusible or releases a diffusible dye, or (2) the compound represented by formula (I) which is inherently diffusible is rendered non-diffusible. This change occurs when Y is oxidized or when it is reduced depending upon the nature of Y. The two cases may be properly selected.
  • Examples of a substance of formula (I) whose diffusibility changes by oxidation of Y include so-called dye releasing redox substrates, such as p-sulfonamidonaphthols (including p-sulfonamidophenols; specific examples are described in Japanese Patent Application (OPI) No. 33,826/73 (corresponding to U.S. Pat. Nos. 3,928,312) and 50,736/78, and European Patent Application (OPI) No. 76,492), o-sulfonamidophenols (including o-sulfonamidonaphthols; specific examples are described in Japanese Patent Application (OPI) Nos. 113,624/76 (corresponding to U.S. Pat. No.
  • dye releasing redox substrates such as p-sulfonamidonaphthols (including p-sulfonamidophenols; specific examples are described in Japanese Patent Application (OPI) No. 33,826/73
  • Another example includes the intramolecular assist-type substrates described in Japanese Patent Application (OPI) No. 20,735/82 (corresponding to U.S. Pat. No. 4,358,532) and Japanese Patent Application (OPI) No. 65,839/84 which release dyes to intramolecular nucleophilic attach after the oxidation of Y.
  • OPI Japanese Patent Application
  • No. 65,839/84 Japanese Patent Application
  • Still another example includes substrates which release dyes by an intromolecular cyclizing reaction under basic conditions but substantially fail to release dyes upon oxidation of Y (specific examples are given in Japanese Patent Application (OPI) No. 63,618/76 (corresponding to U.S. Pat. No. 3,980,479).
  • substrates which release dyes by a reaction of the isooxazolone ring under the action of nucleophilic reagents are also useful.
  • a further example includes substrates which under basic conditions liberate the dye moiety by dissociation of acid protons, but substantially fail to release dyes upon oxidation of Y (specific examples are given in Japanese Patent Application (OPI) Nos. 69,033/78 and 130,929/79 (corresponding to U.S. Pat. No. 4,232,107).
  • OPI Japanese Patent Application
  • Examples of substances whose diffusibility changes upon the reduction of Y include the nitro compounds described in Japanese Patent Application (OPI) No. 110,827/78 (corresponding to U.S. Pat. No. 4,139,379) and the quinone compounds described in Japanese Patent Application (OPI) No. 110,827/78 and U.S. Pat. Nos. 4,356,249 and 4,358,525. These compounds are reduced with the reducing agent (referred to as the electron donor) remaining unconsumed in the thermodevelopment process, and by the intramolecular attack of the resulting nucleophilic group, they release dyes.
  • the reducing agent referred to as the electron donor
  • a useful variety of this example involves quinone-type substrates which permit liberation of a dye moeity by the dissociation of the acid protons of the reduction product (specific examples of such substrate are described in Japanese Patent Application (OPI) Nos. 130,927/79 and 164,343/81 (corresponding to U.S. Pat. No. 4,371,604).
  • any dye donating substance can be used so long as the color of the image formed on a dye fixing layer satisfies the above-described definition.
  • the present invention can be especially preferably practiced by including at least one yellow dye donating substance, at least one magenta dye donating substance and at least one cyan dye donating substance selected from the above-exemplified image-forming dyes into a layer containing a silver halide and optionally an organic silver salt oxidizing agent or a layer adjacent to this layer.
  • the amount of each of the dye donating substances is desirably from 0.01 to 4 moles per mole of silver (in silver halide and an organic silver salt) in each silver halide emulsion layer.
  • the ratio of the amounts of the dye donating substances may be selected so that when the dyes are fixed to the dye fixing layer, values of a* and b* of the color of the image come within the aforesaid range.
  • the dye donating substances may be incorporated (1) in the silver halide photographic layer, (2) in a layer adjacent to the silver halide photographic layer (hereinafter referred to as an adjacent layer), (3) or they may be divided into two portions and incorporated in both of these layers.
  • the photographic material of the present invention may have two or more of silver halide layers having the same color sensitivity and each dye donating substances or each portion of divided dye donating substances (may be a mixture) may be incorporated to each silver halide photographic layer or (5) at least one of the silver halide emulsion layers has an adjacent layer containing at least one dye donating substance.
  • a silver halide emulsion layer has an adjacent layer, it is preferable that the silver halide emulsion layer is coated on the adjacent layer.
  • the layer containing a dye donating substance which absorbs light having a wavelength within the range to which the silver halide is sensitive is provided on a support firstly as the lowest layer.
  • the interlayer comprises a binder which can be used in the silver halide photographic layer.
  • An organic silver salt may also be incorporated in the silver halide emulsion layer, if desired.
  • the adjacent layer further comprises a binder such as that used in the silver halide emulsion layer.
  • the dye donating substances differ in dye releasing reactions depending upon their structures, and this difference is especially large in the dry image-forming process. It was previously thought that if a black or gray color image is formed by mixing these substances, a difference in hue would arise between high density portions and low density portions, thus causing problems in practical applications. It has now been found that if the color hue is within the range specified in the present invention by human observations, the image does not look particularly colored, but assumes a pleasing achromatic color. The present invention is based on this discovery.
  • the color of a dye to be released can be anticipated. Accordingly, one can determine the ratio of amounts of the dye donating substances which will give the aforesaid range in the chromaticity diagram.
  • the dye donating substances can be introduced into a layer of the photographic material by known method such as the method described in U.S. Pat. No. 2,322,027. At this time, high-boiling and low-boiling organic solvents can be used.
  • the high boiling solvents include alkyl phthalates such dibutyl phthalate and dioctyl phthalate, phosphates such as diphenyl phosphate, triphenyl phosphate, tricresyl phosphate and dioctyl butyl phosphate, citrates such as tributyl acetylcitrate, benzoates such as octyl benzoate, alkylamides such as diethyllaurylamide, fatty acid esters such as dibutoxyethyl succinate and dioctyl azelate, and trimesates such as tributyl trimesate.
  • alkyl phthalates such dibutyl phthalate and dioctyl phthalate
  • phosphates such as diphenyl phosphate, triphenyl phosphate, tricresyl phosphate and dioctyl butyl phosphate
  • citrates such as tributyl
  • low boiling organic solvents having a boiling point of from about 30° to 160° C. include lower alkyl acetates such as ethyl acetate and butyl acetate, ethyl propionate, sec-butyl alcohol, methyl isobutyl ketone, ⁇ -ethoxyethyl acetate, methyl cellosolve acetate and cyclohexanone.
  • a mixture of high-boiling organic solvent and lower-boiling organic solvent may be used.
  • the above dye donating substances are dissolved in such solvents and dispersed in a hydrophilic colloid.
  • the method of dispersing by using polymers such as those described in Japanese Patent Publication No. 3,9853/76 and Japanese Patent Application (OPI) No. 59,943/76 may also be used.
  • Various surface-active agents can be used when dispersing the dye donating substances in a hydrophilic colloid. Examples of surface-active agents used for this purpose include those compounds cited as surface-active agents elsewhere in the specification.
  • the amount of the high-boiling organic solvent used in this invention is not more than 10 g, preferably not more than 5 g, per gram of the dye donating substance.
  • Examples of the reducing agent used in this invention include hydroquinone compounds (such as hydroquinone, 2,5-dichlorohydroquinone and 2-chlorohydroquinone, aminophenol compounds (such as 4-aminophenol, N-methylaminophenol, 3-methyl-4-aminophenol and 3,5-dibromoaminophenol), catechol compounds (such as catechol, 4-cyclohexylcatechol, 3-methoxycatechol and 4-(N-octadecylamino) catechol), and phenylenediamine compounds (such as N,N-diethyl-p-phenylenediamine, 3-methyl-N,N-diethyl-p-phenylenediamine, 3-methoxy-N-ethyl-N-ethoxy-p-phenylenediamine and N,N,N',N'-tetramethyl-p-phenylenediamine).
  • hydroquinone compounds such as hydroquinone, 2,5-dichlor
  • Examples of preferred reducing agents for use in this invention include 3-pyrazolidone compounds (such as 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone, 1-m-tolyl-3-pyrazolidone, 1-p-tolyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1-phenyl-4,4-bis(hydroxymethyl)-3-pyrazolidone, 1,4-dimethyl-3-pyrazolidone, 4-methyl-3-pyrazolidone, 4,4-dimethyl-3-pyrazolidone, 1-(3-chlorophenyl)-4-methyl-3-pyrazoline, 1-(4-chlorophenyl)-4-methyl-3-pyrazoline, 1-(4-tolyl)-4-methyl-3-pyrazoline, 1-(2-tolyl)-4-methyl-3-pyrazolidone, 1-(4
  • the preferable amount of the reducing agent added in this invention is from 0.01 to 20 moles, especially preferably from 0.1 to 10 moles per mole of silver of silver halide and an organic silver salt.
  • auxiliary developing agent is a substance when oxidized with the silver halide, has the ability to oxidize a reducing substrate in the dye donating substance.
  • Useful auxiliary developing agents include hydroquinone, alkyl-substituted hydroquinones such as t-butylhydroquinonne and 2,5-dimethylhydroquinone, catechols, pyrogallols, halogen-substituted hydroquiones such as chlorohydroquinone or dichlorohydroquinone, alkoxy-substituted hydroquionones such as methoxyhydroquinone, polyhydroxybenzene derivatives and methylhydroxynaphthalene.
  • hydroquinone alkyl-substituted hydroquinones such as t-butylhydroquinonne and 2,5-dimethylhydroquinone
  • catechols pyrogallols
  • halogen-substituted hydroquiones such as chlorohydroquinone or dichlorohydroquinone
  • alkoxy-substituted hydroquionones such as methoxyhydroquinone, polyhydroxybenz
  • methyl gallate ascorbic acid, ascorbic acid derivatives, hydroxylamines such as N,N'-di-(2-ethoxyethyl)hydroxylamine, pyrazolidones such as 1-phenyl-3-pyrazolidone and 4-methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidones, reductones and hydroxytetronic acids.
  • the auxiliary developing agent can be used in a predetermined concentration.
  • concentration range is from 0.0005 to 20 moles, and especially 0.001 to 4 moles, per mole of silver of silver halide and an organic silver salt.
  • the silver halides used in this invention are, for example, silver chloride, silver chlorobromide, silver chloroiodide, silver bromide, silver iodobromide, silver chloroiodobromide, and silver iodide.
  • Such a silver halide for example silver iodobromide
  • a silver halide for example silver iodobromide
  • the average grain size of the silver halide grains used in this invention is preferably from 0.001 ⁇ m to 10 ⁇ m, and especially preferably from 0.001 ⁇ m to 5 ⁇ m.
  • the silver halide used in this invention may be used as is. If desired, it may be chemically sensitized with a chemical sensitizer such as a compound of sulfur, selenium, or tellurium, or a compound of gold, platinum, palladium, rhodium or iridium, or a reducing agent such as a tin halide, or a combination thereof. Details of chemical sensitization are described in T. H. James, The Theory of the Photographic Process, 4th Edition, Chapter 5, pages 149-169, Macimillan Publishing Co., Inc., 1977.
  • the suitable total amount of the photosensitive silver halide coated in this invention is 1 mg/m 2 to 10 g/m 2 as silver.
  • An especially preferred embodiment of this invention involves the joint use of an organic silver salt.
  • the organic silver salt When heated in the presence of the exposed silver halide to a temperature of at least 80° C., preferably at least 100° C., the organic silver salt reacts with the dye donating image-forming substance or with a reducing agent to be optionally present together with the image-forming substance to form a silver image.
  • the conjoint use of the organic silver salt oxidizing agent can give a photographic material which develops a color in a high density.
  • organic silver salt oxidizing agents examples include those described hereinafter.
  • silver salts of organic compounds having a carboxyl group can be cited.
  • Typical examples are silver salts of aliphatic carboxylic acids and silver salts of aromatic carboxylic acids.
  • Silver salts having a mercapto or thione group and silver salts of the derivatives of such compounds may also be cited.
  • Silver salts of compounds having an imino group can also be cited.
  • examples include silver salts of the benzotriazole and its derivatives described in Japanese Patent Publication Nos. 30,270/69 and 18,416/70, such as a silver salt of benzotriazole, silver salts of alkyl-substituted benzotriazoles such as methylbenzotriazole, silver salts of halogen-substituted benzotriazoles such as 5-chlorobenzotriazole, and silver salts of carboimidobenzotriazoles such as butylcarboimidobenzotriazole; and the silver salts of 1,2,4-triazole or 1-H-tetrazole silver salt, carbazole silver salt, saccharin silver salt and silver salts of imidazole or imidazole derivatives described in U.S. Pat. No. 4,220,709.
  • the silver salts and organic metal salts such as copper sterate described in Research Disclosure, No. 170, 17029, are metal salt oxidizing agents which can also be used in this invention.
  • the suitable total coating amount of the photo-sensitive silver halide and the organic silver salt is from 50 mg/m 2 to 10 g/m 2 as silver.
  • Binders may be used singly or in combination in this invention.
  • a hydrophilic binder may be used.
  • Typical hydrophilic binders are transparent or semitransparent hydrophilic binders, and include organic substances, for example, proteins such as gelatin, gelatin derivatives and cellulose derivatives and polysaccharides such as a starch and gum arabic, and synthetic polymers such as water-soluble polyvinyl compounds (e.g., polyvinylpyrrolidone and polyacrylamide).
  • Other synthetic polymers include dispersed polymeric vinyl compounds in the form of a latex which particularly increase the dimensional stability of photographic materials.
  • compounds can be used which can simultaneously activate the developement and stabilize the images formed.
  • examples of a preferred group of such compounds include the isothiuroniums typified by 2-hydroxyethyl isothiuronium trichloroacetate described in U.S. Pat. No. 3,301,678, bis-isothiuroniums such as 1,8-(3,6-dioxaoctane)bis(idothiuronium trichloracetate) described in U.S. Pat. No. 3,669,670, the thiol compounds described in West German Patent Application (Laid Open) No.
  • the thiazolium compounds such as 2-amino-2-thiazolium trichloroacetate and 2-amino-5-bromoethyl-2-thiazolium trichloroacetate described in U.S. Pat. No. 4,012,260, the compounds having ⁇ -sulfonyl acetate as an acid moiety, such as bis(2-amino-2-thioazolium) methylenebis(sulfonyl acetate) and 2-amino-2-thiazolium phenyl sulfonyl acetate, described in U.S. Pat. No. 4,060,420, and the compounds having 2-carboxycarboxiamide as an acid moiety described in U.S. Pat. No. 4,088,496.
  • the compounds having ⁇ -sulfonyl acetate as an acid moiety such as bis(2-amino-2-thioazolium) methylenebis(sulfonyl acetate) and 2-amino-2
  • azole thioethers and blocked azolinethione compounds described in Belgian Pat. No. 768,071, the 4-aryl-1-carbamyl-2-tetrazoline-5-thione compounds described in U.S. Pat. No. 3,898,859, and compounds described in U.S. Pats. Nos. 3,839,041, 3,844,788 and 3,877,940.
  • various dye releasing aids can be used.
  • the dye releasing aids are compounds showing basicity and capable of activating the development or so-called mucleophilic compounds.
  • Bases or base precursors are used.
  • the dye releasing aid can be used both in the photographic material and in the dye fixing material.
  • Base precursors are advantageous for use in the photographic material.
  • the base precursors are compounds which release base components when heated.
  • the base components to be released may be inorganic or organic bases.
  • Examples of preferred bases include inorganic bases such as hydroxides, secondary or tertiary phosphates, borates, carbonates, quinolinates and metaborates of alkali metals or alkaline earth metals, ammonium hydroxides, and other metal hydroxides, and organic bases such as quaternary alkylammonium hydroxides, aliphatic amines (trialkylamines, jydroxylamines and aliphatic polyamines), aromatic amines (N-alkyl-substituted aromatic amines, N-hydroxyalkylsubstituted aromatic amines and bis[p-(dialkylamino)-phenyl] methanes), heterocyclic amines, amidines, cyclic amidines, guanidines and cyclic guanidines.
  • inorganic bases such as hydroxides, secondary or tertiary phosphates, borates, carbonates, quinolinates and metaborates of alkali
  • base precursors Compounds which when heated, induce some reaction and release bases are used as the base precursors, and include, for example, salts of organic acids and bases which when heated, decarboxylated and decomposed, and compounds which are decomposed and release an amine by the Lossen rearrangement, the Beckmann rearrangement, etc.
  • Preferred base precursors are precursors of the aforesaid organic bases.
  • salts with heatdecompsable organic acids such as trichloroacetic acid, trifluoroacetic acid, propiolic acid, cyanoacetic acid, sulfonylacetic acid and acetoacetic acid, and the salts with 2-carboxycarboxamide described in U.S. Pat. No. 4,088,496.
  • Examples of compounds considered to release bases by the decarboxylation of the acid moiety include trichloroacetic acid derivatives such as guanidinetrichloroacetic acid, piperidinetrichloroacetic acid, morpholinetrichloroacetic acid, p-toluidinetrichloroacetic acid and 2-picolinetrichloroacetic acid.
  • trichloroacetic acid derivatives such as guanidinetrichloroacetic acid, piperidinetrichloroacetic acid, morpholinetrichloroacetic acid, p-toluidinetrichloroacetic acid and 2-picolinetrichloroacetic acid.
  • Examples of preferred base precursors other than trichloroacetic acids include the 2-carboxycarboxamide derivatives described in U.S. Pat. No. 4,088,946, the ⁇ -sulfonyl acetate derivatives described in U.S. Pat. No. 4,060,420 and the salts of propiolic acid derivatives with bases described in Japanese Patent Application No. 55,700/83.
  • salts of alkali metals and alkaline earth metals are also effective as the base components, and such salts are described in Japanese Patent Application No. 69,597/83.
  • the amount of such a base or base precursor can be used in amounts within a broad range.
  • the useful range is not more than 50% by weight, preferably 0.01 to 40% by weight, based on the total weight of the dry coating of the photographic material.
  • bases or base precursors can be used not only for promoting dye releasing, but also for other purpose, for example for adjusting the pH value.
  • thermodevelopable photographic material of this ivnention can be disposed at any suitable positions.
  • one or more of the components may be disposed in one or more layers of the photographic material.
  • thermodevelopable photographic material of this invention is effective for formation of a negative or positive image.
  • the formation of a negative or positive image will depend mainly upon the selection of specified photosensitive silver halides and the type of the dye donating substance.
  • the internal image silver halide emulsions described in U.S. Pat. Nos. 2,592,250, 3,206,313, 3,367,778 and 3,447,927, or mixtures of the internal image silver halides and surface image silver halide emulsion such as those described in U.S. Pat. No. 2,996,382 can be used.
  • a latent image is obtained by imagewise exposure to radiations including visible light.
  • light sources used are those ordinarily used for color prints, for example, a tungsten lamp, a mercury lamp, a halogen lamp such as an iodine lamp, a xenone lamp, a laser beam, a CRT light sources, a fluorescent tube and a light emitting diode.
  • Means of heating may be a simple hot plate, an iron, a hot roller, or a heat-generating body or the like utilizing carbon or titanium white.
  • the silver halide used in this invention may be spectrally sensitized with methine dyes or other dyes.
  • dyes examples include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolor cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes.
  • Especially useful dyes are cyanine dyes, merocyanine dyes and complex merocyanine dyes. Any nuclei usually employed in cyanine dyes may be applied as basic heterocyclic nuclei.
  • Examples are a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus and a pyridine nucleus; nuclei resulting from fusion of alicyclic hydrocarbon rings with these nuclei; and nuclei resulting from fusion of these nuclei with aromatic hydrocarbon rings, such as an indolenine nucleus, a benzindolenine nucleus, an indole nucleus, a benzaxazole nucleus, a naphthoxazole necleus a naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, and a quinoline nucleus.
  • Five to six-membered heterocyclic nuclei such as pyrazoline-5-one, thiohydantoin, 2-thiooxazolidine-2,4-dione, thiazolidine-2,4-dione, rhodanine and thiobarbitul nuclei may be applied to merocyanine dyes or complex merocyanine dyes as nuclei having a ketomethylene structure.
  • sensitizing dyes may be used singly or in combination. Combinations of sensitizing dyes are frequently used for the purpose of supersensitization. Typical examples are described in U.S. Pat. Nos. 2,688,545, 2,977,229, 3,397,060, 3,522,052, 3,527,641, 3,617,293, 3,628,964, 3,666,480, 3,672,898, 3,679,428, 3,703,377, 3,769,301, 3,814,609, 3,837,862, and 4,026,707, British Pat. Nos. 1,344,281 and 1,507,803, Japanese Patent Publications Nos. 4,936/68 and 12,375/78, Japanese Patent Application (OPI) Nos. 110,618/77 and 109,925/77.
  • OPI Japanese Patent Application
  • a dye having no spectral sensitizing activity or a substance which does not substantially absorb visible light and causes supersensitization may be included into an emulsion.
  • aminostyryl compounds substituted by nitrogen-containing heterocyclic group such as those described in U.S. Pat. Nos. 2,933,390 and 3,635,721
  • aromatic organic acid/formaldehyde condensate such as those described in U.S. Pat. No. 3,743,510
  • cadmium salts and azaindene compounds may be included.
  • the combinations described in U.S. Pat. Nos. 3,615,m613, 3,615,641, 3,617,295 and 3,635,721 are especially useful.
  • a support which can withstand processing temperatures is used in the photographic material of this invention, and a color fixing material.
  • Supports generally used include not only glass, paper, metals, and the like, but also films such as acetylcellulose, cellulose ester, polyvinyl acetal, polystyrene, polycarbonate and polyethylene terephthalate films.
  • a paper support to which a polymer such as polyethylene is laminated may also be used.
  • the polyesters described in U.S. Pat. Nos. 3,634,089 and 3,725,070 are preferably used.
  • thermodevelopable silver halide photographic material of the present invention is composed of a support having thereon a photographic layer(s) (I) containing silver halide, a dye donating substance and a binder, and a dye fixing layer (II) capable of receiving the mobile dye formed in the photographic layer (I).
  • the above described photographic layer (I) and the dye fixing layer (II) may be formed on the same support, or they may be formed on different supports, respectively.
  • the dye fixing layer (II) can be stripped off the photographic layer (I).
  • the thermodevelopable photographic material is exposed imagewise to light, it is developed by heating uniformly and thereafter the dye fixing layer (II) or the photographic layer (I) is peeled apart.
  • a photographic material having the photographic layer(s) coated on a support and a fixing material having the dye fixing layer (II) coated on a support are separately formed and they are superposed so that the layers are contacted to each other, after the photographic material is exposed imagewise to light and uniformly heated, the mobile dye is transferred on the dye fixing layer (II).
  • the dye fixing layer (II) can contain, for example, a dye mordant in order to fix the dye.
  • a dye mordant in order to fix the dye.
  • various mordants can be used, and polymer mordants are particularly preferred.
  • the dye fixing layer may contain the bases, base precursors and thermal solvents.
  • Polymer mordants used in the present invention are polymers containing secondary and tertiary amino groups, polymers containing nitrogen-containing heterocyclic moieties, polymers having quaternary cation groups thereof, having a molecular weight of from 5,000 to 200,000, and particularly from 10,000 to 50,000.
  • vinylpyridine polymers and vinylpyridinium cation polymers as disclosed in U.S. Pat. Nos. 2,548,564, 2,484,430, 3,148,061 and 3,756,814, etc.
  • polymer mordants capable of cross-linking with gelatin as disclosed in U.S. Pat. Nos. 3,625,694, 3,859,096 and 4,128,538, British Pat. No. 1,277,453, etc.
  • aqueous sol type mordants as disclosed in U.S. Pat. Nos. 3,958,995, 2,721,852 and 2,798,063, Japanese Patent Application (OPI) Nos.
  • mordants disclosed in U.S. Pat. Nos. 2,675,316 and 2,882,156 can be used.
  • mordants capable of cross-linking with a matrix such as geletin, water-insoluble mordants, and aqueous sol (or latex dispersion) type mordants are preferably used.
  • Polymers having quaternary ammonium groups and groups capable of forming covalent bonds with geletin for example, aldehydo groups, chloroalkanoyl groups, chloroalkyl groups, vinylsulfonyl groups, pyridiniumpropionyl groups, vinylcarbonyl groups, alkylsulfonoxy groups, etc.
  • geletin for example, aldehydo groups, chloroalkanoyl groups, chloroalkyl groups, vinylsulfonyl groups, pyridiniumpropionyl groups, vinylcarbonyl groups, alkylsulfonoxy groups, etc.
  • (a) is ##STR5## wherein X represents a hydrogen atom, an alkyl group or a halogen atom (the alkyl group may be substituted);
  • (b) is an acrylic ester
  • Water-insoluble polymers wherein at least 1/3 of the repeating units are those represented by the following general formula ##STR6## wherein R 1 b , R 2 b and R 3 b each represents an alkyl group, with the total number of carbon atoms included being 12 or more (the alkyl group may be substituted), and X.sup. ⁇ represents an anion.
  • gelatins can be employed as a binder for the mordant layer.
  • gelatin which is produced in a different manner such lime-processed gelatin, acid-possessed gelatin, etc., or a gelatin derivative which is prepared by chemically modifying gelatin such as phthalated gelatin, sulfonylated gelatin, etc., can be used.
  • gelatin subjected to a desalting treatment can be used, if desired.
  • the ratio of polymer mordant to gelatin and the amount of the polymer mordant coated can be easily determined by one skilled in the art depending on the amount of the dye to be mordanted, the type and composition of the polyer mordant and further on the image-forming process used.
  • the ratio of mordant to gelatin is from 20/80 to 80/20 (by weight) and the amount of the mordant coated is from 0.5 to 8 g/m 2 .
  • the dye fixing layer (II) can have a white reflective layer.
  • a layer of titanium dioxide dispersed in gelatin can be provided on the mordant layer on a transparent support.
  • the layer of titanium dioxide forms a white opaque layer, by which reflection color images of the transferred color images which is observed through the transparent support is obtained.
  • Typical dye fixing material used in the present invention is obtained by mixing the polymer containing ammonium salt groups with gelatin and applying the mixture to a transparent support.
  • fixing material it is not necessary that the fixing material to be white, i.e., fixing material having a pale color may also be used.
  • the photographic material and dye fixing material in accordance with this invention may include an inorganic or organic hardening agent in the photographic emulsion layer or a binder layer.
  • the hardening agent include chromium salts (such as chromium alum and chromium acetate), aldehydes (such as formaldehyde, glyoxal and glutaraldehyde), N-methylol compounds (such as dimethylolurea and methyloldimethyl hydantoin), dioxane derivatives (such as 2,3-dihydroxydioxane), active vinyl compounds (such as 1,3,5-triacryloyl-hexahydro-s-triazine), 1,3-vinylsulfonyl-2-propanol), active halogen compounds (such as 2,4-dichloro-6-hydroxy-s-triazine), and muchohalogenic acids (such as mucochloric acid and mucophenoxychloric acid). They may
  • a dye diffusion promoting aid may be used for diffusing a dye from the photosensitive layer to the dye fixing layer.
  • Water or a basic aqueous solution containing sodium hydroxide, potassium hydroxide or an inorganic alkali metal salt is used as the dye moving aid in a method involving supplying the moving aid from outside.
  • a low-boiling solvent such as methanol, N,N-dimethylformamide, acetone or diisobutyl ketone, or a mixture of such a low boiling solvent and water or a basic aqueous solution is used.
  • the dye moving air may be used by wetting an image receiving layer with the aid.
  • the moving aid is included in the photographic material or the dye fixing material, there is no need to supply it from outside.
  • the moving aid may be included in the form of the water of crystallization or microcapsules into the material. Alternatively, it may be included as a precursor which releases the solvent at high temperatures.
  • a hydrophilic solvent which is solid at room temperature but dissolves at a high temperature is included in the photographic material or the dye fixing material.
  • the hydrophilic solvent may be included into one or both of the photographic material and the dye fixing material. If may be included into any of an emulsion layer, an intermediate layer, a protective layer and a dye fixing layer, preferably the dye fixing layer and/or a layer adjacent to the dye fixing layer.
  • hydrophilic heat-solvent examples include ureas, pyridines, amides, sulfonamides, imides, alcohols, oximes and other heterocyclic compounds.
  • the photographic material of this invention may further include other compounds, such as sulfamide derivatives, cationic compounds having, for example, a pyridinium group, a surface active agents having a polyethylene oxide chain, sensitizing dyes, anti-halation and anti-irradiation dyes, hardeners, and mordanting dyes which are described, for example, in European patent Applications (OPI) Nos. 76,492 and 6,282, West German Pat. No. 3,315,485, and Japanese Patent Applications Nos. 28,928/83 and 26,008/83.
  • OPI European patent Applications
  • Each of the dye donating substances Y-1, M-1 and C-2 was weighed to each of the amounts indicated in column 1 of Table 1, and 0.5 g of 2-ethylhexyl succinate sodium sulfonate and 5 g of tricresyl phosphate (TCP) were added. Then, 30 ml of ethyl acetate was added, and the mixture was heated to about 60° C. to form a uniform solution. The solution was mixed with stirring with 100 g of a 10% aqueous solution of lime-treated gelatin, and the mixture was homogenized at 10,000 rpm for 10 minutes to obtaina dispersion (I).
  • TCP tricresyl phosphate
  • Dispersions (II) to (VI) were prepared respectively by the same procedure as above except that Y-1, M-1 and C-2 were used in the amounts indicated in columns 2-6 of Table 1.
  • Photographic materials B to F were respectively prepared in the same way as in the preparation of the photographic material A by using dispersions (II) to (VI) instead of the dispersion (I).
  • a 1/1 (by weight) mixture of polyacrylic acid (the degree of polymerization 2000) and polyvinyl alcohol was coated to a thickness of 2 g/m 2 on a paper support laminated with polyethylene having titanium dioxide dispersed therein. On top of it was coated to a wet thickness of 70 ⁇ m a mixed solution prepared by uniformly mixing 100 g of a 10% aqueous solution of poly(methyl acrylate-co-N,N,N-trimethyl-N-vinyl benzyl ammonium chloride) (having a molar ratio of methyl acrylate/vinyl benzyl ammonium chloride of 1/1), 120 g of a 10% polyvinyl alcohol (the saponification degree 18%, the degree of polymerization 2000) 10 g of urea and 26 g of N-methylurea. The coated layer was dried to obtain a dye fixing material.
  • the photographic material A was exposed imagewise at 200 lux for 10 seconds by using a tungsten-filament lamp, and then unfiormly heated for 20 seconds on a heat block heated at 140° C.
  • the above dye fixing material impregnated with water was superimposed on the photographic material so that the coated surfaces contacted. Thirty seconds later, the image-receiving material was peeled off from the photographic material. An image which is positive with respect to the silver image was obtained on the image receiving material.
  • the resulting image was subjected to colorimetry at a reflection density of 0.5 and 1.2 by means of a color analyzer (Type 670 made by Hitachi Limited). The measured data and the results of visual evaluation are shown in Table. 2.

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5817452A (en) * 1996-09-19 1998-10-06 Fuji Photo Film Co., Ltd. Heat developable color light-sensitive material
US6114080A (en) * 1993-12-21 2000-09-05 Eastman Kodak Company Chromogenic black and white imaging for heat image separation

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0246449A (ja) * 1988-08-08 1990-02-15 Fuji Photo Film Co Ltd 熱現像カラー感光材料

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3531286A (en) 1966-10-31 1970-09-29 Minnesota Mining & Mfg Light-sensitive,heat developable copy-sheets for producing color images
US3647437A (en) 1970-12-18 1972-03-07 Polaroid Corp Photographic products, processes and compositions
US4235957A (en) 1979-01-25 1980-11-25 Eastman Kodak Company Thermal silver-dye bleach element and process
US4439513A (en) 1981-12-29 1984-03-27 Fuji Photo Film Co., Ltd. Color photographic light-sensitive material with naphthol redox dye releaser
US4463079A (en) 1981-04-30 1984-07-31 Fuji Photo Film Co., Ltd. Heat developable color photographic materials with redox dye releasers
US4474867A (en) 1981-05-12 1984-10-02 Fuji Photo Film Co., Ltd. Heat-developable color photographic material

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3761270A (en) * 1971-09-27 1973-09-25 Eastman Kodak Co Photographic element composition and process
US4138265A (en) * 1977-06-27 1979-02-06 Eastman Kodak Company Antifoggants in certain photographic and photothermographic materials that include silver salts of 3-amino-1,2,4-mercaptotriazole
US4137079A (en) * 1978-04-03 1979-01-30 Eastman Kodak Company Antifoggants in heat developable photographic materials
JPS5840551A (ja) * 1981-09-02 1983-03-09 Fuji Photo Film Co Ltd カラ−画像形成方法
JPS59159161A (ja) * 1983-03-01 1984-09-08 Konishiroku Photo Ind Co Ltd 熱現像カラ−拡散転写感光材料

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3531286A (en) 1966-10-31 1970-09-29 Minnesota Mining & Mfg Light-sensitive,heat developable copy-sheets for producing color images
US3647437A (en) 1970-12-18 1972-03-07 Polaroid Corp Photographic products, processes and compositions
US4235957A (en) 1979-01-25 1980-11-25 Eastman Kodak Company Thermal silver-dye bleach element and process
US4463079A (en) 1981-04-30 1984-07-31 Fuji Photo Film Co., Ltd. Heat developable color photographic materials with redox dye releasers
US4474867A (en) 1981-05-12 1984-10-02 Fuji Photo Film Co., Ltd. Heat-developable color photographic material
US4439513A (en) 1981-12-29 1984-03-27 Fuji Photo Film Co., Ltd. Color photographic light-sensitive material with naphthol redox dye releaser

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Research Disclosure 17326, pp. 49-51, Sep. 1978.

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6114080A (en) * 1993-12-21 2000-09-05 Eastman Kodak Company Chromogenic black and white imaging for heat image separation
US5817452A (en) * 1996-09-19 1998-10-06 Fuji Photo Film Co., Ltd. Heat developable color light-sensitive material

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