USH691H - Heat developable photographic element - Google Patents

Heat developable photographic element Download PDF

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Publication number
USH691H
USH691H US07/153,535 US15353588A USH691H US H691 H USH691 H US H691H US 15353588 A US15353588 A US 15353588A US H691 H USH691 H US H691H
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Prior art keywords
dye
light
heat
layer
sensitive
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Hiroshi Kitaguchi
Masatoshi Kato
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/494—Silver salt compositions other than silver halide emulsions; Photothermographic systems ; Thermographic systems using noble metal compounds
    • G03C1/498—Photothermographic systems, e.g. dry silver
    • G03C1/49836—Additives
    • G03C1/49845—Active additives, e.g. toners, stabilisers, sensitisers

Definitions

  • the present invention relates to a heat-developable photographic element, and particularly, to a heat-developable photographic element having stable photographic properties irrespective of changes in developing treatment conditions.
  • a photographic process using silver halide has heretofore been most widely used because it is superior to other photographic processes such as electrophotography and diazo photography in photographic characteristics such as sensitivity and control of gradation.
  • a technique for forming images rapidly and in a simplified manner has been developed, in which a light-sensitive material containing silver halide is not wet-developed with a developer, for example, but is dry-developed, for example, by heating.
  • a heat-developable light-sensitive material is known in the art and is described in, for example, Shashin Kogaku no Kiso (Fundamentals of Photographic Engineering), pp. 553-555 (Corona Co., Ltd., Tokyo, 1979), Eizo Joho (Image Information), April 1978, p. 40, Nebletts Handbook of Photography and Reprography, pp. 32-33 (7th Ed., Van Nostrand Reinhold Company, 1977), U.S. Pat. Nos. 3,152,904, 3,301,678, 3,392,020, 3,457,075, British Pat. Nos. 1,131,108, 1,167,777, and Research Disclosure, June, 1978, pp. 9-15 (RD-17029).
  • U.S. Pat. No. 3,531,286 discloses a combination of a p-phenylenediamine reducing agent and a phenolic or active methylene coupler
  • U.S. Pat. No. 3,761,270 discloses a p-aminophenol-based reducing agent
  • Belgian Pat. No. 802,519 and Research Disclosure, Sept. 31, 1975, p. 32 disclose a sulfonamidophenol-based reducing agent
  • U.S. Pat. No. 4,021,240 discloses a combination of a sulfonamidophenol-based reducing agent and a 4-equivalent coupler.
  • Another method forms positive color images by the light-sensitive silver/dye bleaching process.
  • useful dyes and a bleaching method are described in, for example, Research Disclosure, April, 1976, pp. 30-32 (RD-14433), ibid., December, 1976, pp. 14-15 (RD-15227), and U.S. Pat. No. 4,235,957.
  • a heat-developable light-sensitive material is developed by heating with a base as a development accelerator.
  • a base as a development accelerator.
  • various problems arise. For example, once a heat-developable light-sensitive material is heated to a high temperature, a long time is required for the temperature to return to an ordinary temperature. As a result, the material is developed excessively and image quality is decreased. Furthermore, even if the same heating pattern is applied for development, slight changes in conditions such as outer temperature, heating temperature, water content of the light-sensitive material, and time produce undesirable variations in development.
  • An object of the present invention is to provide a novel heat-developable light-sensitive material in which development can be stopped at a suitable time (i.e., a development time having no excessive development and fogged image) without reducing maximum image density, that is, a heat-developable light-sensitive material in which a base resulting from decomposition of a base precursor releases a development inhibitor at a suitable time after the start of development to stop development.
  • a suitable time i.e., a development time having no excessive development and fogged image
  • Another object of the present invention is to provide a heat-developable light-sensitive material which is free from unevenness in image density resulting from variations in heating temperature, i.e., materials having a temperature compensation capability.
  • a heat-developable photographic element comprising a support having thereon a light-sensitive silver halide, a binder, a base precursor and a photographic reagent capable of releasing a compound represented by the general formula (I) by reaction with a base.
  • a heat-developable photographic element comprising a support having thereon a light-sensitive silver halide, a binder, a base precursor and a photographic reagent capable of releasing a compound represented by the general formula (I) by reaction with a base.
  • Y is an atomic group necessary for forming a 5-, 6- or 9-membered heterocyclic ring.
  • the present invention relates to a heat-developable photographic element containing at least a base precursor and a compound capable of releasing a compound represented by the general formula (I) by reaction with a base in a light-sensitive layer and/or an image receiving layer.
  • a blocking group e.g., an acyl group and a sulfonyl group
  • a blocking group releasing a photographic reagent through the reverse Michael reaction as described in Japanese Patent Publication No. 17369/79 and U.S. Pat. Nos. 3,791,830 and 4,009,029
  • a blocking group releasing a photographic reagent with formation of quinone methide or quinone methide-like compounds through intramolecular electron transfer as described in U.S. Pat. Nos.
  • nitrogen-containing heterocyclic compounds having a mercapto group as represented by the general formula (I) have a development inhibiting effect in a silver halide light-sensitive material. It is disclosed in Japanese Patent Application No. 176351/84 (filed on Aug. 24, 1984 by Fuji Photo Film Co., Ltd.) that such nitrogen-containing heterocyclic compounds also have a development inhibiting effect in a heat-developable light-sensitive material. However, if the compound of the general formula (I) is initially present in an emulsion layer, development is generally inhibited from the beginning of development, leading to a reduction in image density and a low sensitivity.
  • a reagent containing a blocked photographically useful group of the compound of the general formula (I) when used in a heat-developable color light-sensitive material, it can release the compound of the general formula (I) by the action of a base released from a base precursor.
  • a base precursor is first decomposed to release a base.
  • development is initiated, and the photographic reagent of the present invention is decomposed by the action of a base at a middle stage to a final stage of development, when the amount of the base formed is increased, thereby releasing a compound of the general formula (I), which has a development inhibiting capability, and stopping the development.
  • a development inhibitor is released and, as a result, an image can be obtained in which a density that could be reached is not reduced and the S/N ratio is high.
  • the heat-developable color light-sensitive material of the present invention has a compensation effect for unevenness in the developing temperature. Since the heat-developable light-sensitive material is usually developed at a temperature of 100° C. or more, slight variations in the temperature of the surface of the light-sensitive material cannot be avoided, and these slight variations cause unevenness in image density. That is, in areas where the temperature is high, rate of development is rapid and thus image density is high, while in areas where the temperature is low, rate of development is slow and thus the image density is low. In the heat-developable light-sensitive material of the present invention, however, the above photographic reagent is rapidly released from the compound of the general formula (I) in such high temperature areas and thus the image density is stopped at a given level. On the other hand, in low temperature areas, the opposite occurs, providing an overall compensation effect for temperature unevenness.
  • base precursors compounds undergoing certain reactions on heating to release a base are preferably used. These compounds include organic acid/base salts which are decomposed with the decarboxylation reaction by heating, and compounds which are decomposed by a reaction (e.g., by an intramolecular nucleophilic substitution reaction, a Lossen rearrangement, or a Beckmann rearrangement), thereby releasing amines.
  • Preferred base precursors include trichloroacetic acid salts as described in British Pat. No. 998,949, c-sulfonylacetic acid salts as described in U.S. Pat. No. 4,060,420, propiolic acid salts as described in Japanese Patent Application No. 55700/83 (corresponding to U.S. Pat.
  • the amount of the base precursor added can be chosen within a wide range.
  • the amount of the base precursor added is preferably 50 wt % or less, more preferably 0.01 to 40 wt %, based on the total weight of the coated layer.
  • the above base precursors can be used as mixtures comprising two or more thereof.
  • Photographic reagents which release a compound of the general formula (I) (hereinafter referred to merely as "A") under the action of the base released from the above base precursor will hereinafter be described in more detail.
  • Y is an atomic group necessary for a 5-, 6- or 9-membered heterocyclic ring.
  • the heterocyclic ring formed by Y contains at least two nitrogen atoms, at least one nitrogen atom and one oxygen atom, or at least one nitrogen atom and one sulfur atom.
  • the heterocyclic ring includes a single ring or a ring which is condensed with a benzene nucleus or a naphthalene nucleus.
  • Z is a hydrogen atom, or a group consisting essentially of at least one group selected from an alkyl group, an aryl group, a cycloalkyl group, an alkenyl group and an aralkyl group, having from 1 to 8 carbon atoms, and preferably a hydrogen atom. Further, these groups may be substituted with a suitable group. Carbon atoms constituting the ring in the formulae may be substituted with a group other than a hydrogen atom.
  • development inhibitor precursors used in the conventional photographic materials are suitable. Of these compounds, the following three types of compounds are preferred.
  • the above reaction releasing A after the attack of the base on the carbon atom of the functional group includes (1) releasing A as a result of cleavage of a bond directly bonded to the carbon atom, (2) releasing A as a result of cleavage of another bond associated with the electron transfer, (3) releasing A as a result of cleavage of another bond due to an intramolecular nucleophilic attack with or without electron transfer, (4) releasing A according to a combination of two or more of the above reactions, and (5) releasing A through a timing group.
  • precursor compounds belonging to type 1 include sulfur releasing antifoggants and development inhibitor precursors described in, for example, Japanese Patent Publication No. 9968/73, Japanese Patent Application (OPI) Nos. 8828/77, 82834/82, U.S. Pat. Nos. 3,311,474 and 3,615,617; precursors releasing A as a result of cleavage of an acetyl group followed by electron transfer or further by decarboxylation described in U.S. Pat. Nos. 3,674,478, 3,685,991, 3,932,480, 3,993,661, Japanese Patent Application (OPI) Nos.
  • precursor compounds belonging to type 2 include precursors releasing A by a "reverse Michael" reaction as described in Japanese Patent Publication No. 44927/80, U.S. Pat. Nos. 4,009,029, 3,791,830, 3,888,677, Japanese Patent Application (OPI) Nos. 105640/84, 105641/84 and 105642/84; and precursors releasing A with the formation of a quinone methide-like compound as a result of the formation of an anion due to dissociation of >N--H or --OH followed by intramolecular electron transfer as described in U.S. Pat. Nos. 3,685,991, 3,674,478, 3,993,661, 3,932,480 and Japanese Patent Application (OPI) Nos. 976/83 and 1139/83, U.S. Pat. Nos. 4,416,977 and 4,420,554.
  • precursor compounds belonging to type 3 include sulfonyl group-containing precursor compounds as described in Japanese Patent Application (OPI) No. 8828/77.
  • the release of A due to the intramolecular electron transfer or intramolecular nucleophilic attack can be conducted through a suitable timing group.
  • Typical examples are the decarboxylation reaction as described in the above references, and the deformylation reaction as described in U.S. Pat. No. 4,522,917.
  • A* is a monovalent group (i.e., ##STR7## of the compound of formula (I) designated by A bonded through the mercapto sulfur atom thereof, R 0 is an aliphatic group, an aryl group, a heterocyclic group, an aryloxy group or a substituted or unsubstituted amino group, having from 1 to 21 carbon atoms, R 1 is an aliphatic group, an aryl group or a heterocyclic group, having from 1 to 21 carbon atoms, and R 2 is a hydrogen atom, an aliphatic group, an aryl group or a heterocyclic group, having from 1 to 21 carbon atoms.
  • Type 1 ##STR8## wherein Y is an atomic group necessary to form a 5- or 6-membered nitrogen-containing heterocyclic ring, ##STR9## wherein X 1 and Z 1 are each an atomic group necessary to form a benzene ring, a naphthalene ring, or a condensed 5- or 6-membered nitrogen-containing hetero ring, T is ##STR10## or --OCH 2 --, and n 1 is 0 or 1, ##STR11##
  • R 3 is a hydrogen group, a group ##STR18## a group ##STR19## or a group ##STR20## wherein R 4 , R 5 , R 6 and R 7 are each an aliphatic group, an aryl group or a heterocyclic group, having from 1 to 21 carbon atoms), Q is an alkyl group or an aryl group, (TIME) is a timing group which releases--A* after being released from the precursor in the form of--TIME) n .sbsb.4 --A*, n 4 is 0 or a positive integer of 1 to 3, R 8 is an aliphatic group, an aryl group, or a heterocyclic group, having from 1 to 21 carbon atoms, R 9 is a hydrogen atom, an aliphatic group, an aryl group or a heterocyclic group, having 1 to 21 carbon atoms, Y, R 1 and A
  • Development inhibitor precursors of the types 1, 2 and 3 as described above can be easily prepared by conventional methods described in the above patents and publications or by conventional methods similar thereto. Several synthesis examples are shown below.
  • the reaction solution became neutral or acidic; that is, its pH dropped to 7 or less. For this reason, a 3N aqueous solution of sodium hydroxide was added to maintain the pH of the reaction solution at 10 or more.
  • the reaction solution was neutralized with hydrochloric acid, cooled to 20° C. and then a precipitate was filtered off and washed with water.
  • the crystals thus obtained contained a small amount of oily material.
  • 93.4 g (0.24 mol) of the desired product was obtained in a pure form.
  • the amount of the development inhibitor precursor used in the photographic element according to the invention varies depending on the type of the precursor or the system in which it is used. In general, it is not more than about 50 wt %, preferably not more than about 30 wt %, based on the total weight of the coated layer. The optimum amount greatly varies depending on the structure of the development inhibitor (I) being released. Some development inhibitors (I), when used in a small amount, accelerate development, whereas when used in a large amount, inhibit development. Thus, when precursors releasing such compounds (I) are added, the initial development is accelerated and the latter half of development is inhibited. Thus, the addition of such precursors is advantageous.
  • the development inhibitor precursor of the present invention is first dissolved in an organic solvent soluble in water (e.g., methanol, ethanol, acetone, and dimethylformamide) or a mixed solution of the organic solvent and water and then incorporated in a binder.
  • an organic solvent soluble in water e.g., methanol, ethanol, acetone, and dimethylformamide
  • the development inhibitor precursor of the present invention can also be incorporated in a binder in the form of finely divided particles.
  • the development inhibitor precursors of the present invention can be used as mixtures comprising two or more thereof.
  • the base precursor and development inhibitor precursor of the present invention can be added to a light-sensitive layer and/or an image receiving layer of the photographic material.
  • the term "light-sensitive layer” as used herein means a heat-developable light-sensitive element or a light-sensitive photographic layer, and also a laminated colloid layer which contains at least one silver halide emulsion layer and may contain an interlayer, a protective layer. A light-insensitive backing layer may be provided on the opposite side of the support from the light-sensitive layer.
  • image receiving layer which is used herein means an image receiving element, further may be a coating layer of a dye fixing element.
  • the base precursor and the development inhibitor precursor may be added to the same layer or to different layers of the photographic material. It is preferred that they are both added to a silver halide emulsion layer.
  • heat-developable photographic element includes both the above heat-developable light-sensitive element and the optionally used dye fixing element, if desired.
  • the heat-developable light-sensitive element of the present invention has at least light-sensitive silver halide, a binder, a base precursor and a photographic reagent capable of releasing a compound of general formula (I) and a reducing agent on a support.
  • a dye providing substance releasing or forming a mobile dye on heating is added.
  • the dye providing substance may have function as a reducing agent.
  • a light-sensitive element and a dye fixing element are essential for the system capable of forming an image by diffusion transfer.
  • These photographic materials generally can be divided into two groups: a system in which the light-sensitive element and the dye fixing element are coated on different supports, and a system in which the light-sensitive element and the dye fixing element are coated on the same support.
  • the system in which the light-sensitive element and the dye fixing element are provided on different supports can further be divided into two groups.
  • One is a type permitting the light-sensitive element and the dye fixing element to be peeled apart from each other, and the other is a unitary type that does not permit the two elements to be separated.
  • the former type after imagewise exposure or heat development, the coating surface of the light-sensitive element and the coating surface of the dye fixing element are brought into contact to transfer an image, and after this image transfer, the light-sensitive element is quickly separated from the dye fixing layer.
  • an opaque or transparent support is selected as the support of the image fixing element. If desired, a white reflection layer may be provided.
  • a white reflection layer is present between the light-sensitive layer of the light-sensitive element and the dye fixing layer of the dye fixing element.
  • This white reflection layer may be provided on the light-sensitive element or the dye fixing element. It is also necessary for the support of the dye fixing element to be transparent.
  • the dye fixing element when present on a support different from that of the light-sensitive element, it is sometimes called a "dye fixing material".
  • the light-sensitive element or dye fixing element may contain an electrically conductive heat generator layer as a heating means for heat development or diffusion transfer of dye.
  • the light-sensitive element of the present invention is required to have at least three silver halide emulsion layers having light sensitivities in different spectral regions.
  • Typical combinations of at least three light-sensitive silver halide emulsions having light sensitivities in different spectral regions are a combination of a blue-sensitive emulsion layer, a green-sensitive emulsion layer, and a red-sensitive emulsion layer; a combination of a green-sensitive emulsion layer, a red-sensitive emulsion layer, and an infrared light-sensitive emulsion layer; a combination of a blue-sensitive emulsion layer, a green-sensitive emulsion layer, and an infrared light-sensitive emulsion layer; and a combination of a blue-sensitive emulsion layer, a red-sensitive emulsion layer, and an infrared light-sensitive emulsion layer.
  • the infrared light-sensitive emulsion layer is an emulsion layer having a sensitivity to light with a wavelength of more than about 700 nm, particularly more than about 740 nm.
  • an emulsion layer having light-sensitivity in a single spectral region may be divided into two or more layers depending on the degree of sensitivity to light of the emulsion.
  • a light-insensitive hydrophilic colloid layer adjacent to the spectrally sensitized emulsion layer (and/or the emulsion layer itself) it is necessary for a light-insensitive hydrophilic colloid layer adjacent to the spectrally sensitized emulsion layer (and/or the emulsion layer itself) to contain a dye providing substance capable of releasing or forming a dye, including a yellow hydrophilic dye, a magenta hydrophilic dye, and a cyan hydrophilic dye.
  • a light-insensitive hydrophilic colloid layer adjacent to each emulsion layer (and/or the emulsion layer itself) it is necessary for a light-insensitive hydrophilic colloid layer adjacent to each emulsion layer (and/or the emulsion layer itself) to contain a dye providing substance releasing or forming a hydrophilic dye having a different color.
  • two or more dye providing substances of the same color may be used as a mixture. Particularly when the dye providing substance is initially colored,
  • auxiliary layers such as a protective layer, an intermediate layer, an antistatic layer, a curl preventing layer, a peeling layer, and a matting layer may be provided.
  • a protective layer usually contains an organic or inorganic matting agent layer for the prevention of adhesion.
  • the protective layer may further contain a mordant, a UV absorbing agent.
  • the protective layer and the intermediate layer may each be composed of two or more layers.
  • the intermediate layer may be incorporated a reducing agent for prevention of color mixing, a UV absorbing agent, and a white pigment (e.g., Ti 02 )
  • a reducing agent for prevention of color mixing e.g., a UV absorbing agent
  • a white pigment e.g., Ti 02
  • the white pigment may be added not only to the intermediate layer but also to the emulsion layer for the purpose of increasing sensitivity.
  • each silver halide emulsion be subjected to dye sensitization using a known sensitizing dye to obtain the desired spectral sensitivity.
  • the dye fixing element that is used in the present invention has at least one layer containing a mordant.
  • a protective layer may be further provided thereon.
  • a water-absorbing layer or a dye transfer aid-containing layer may be provided. These layers may be adjacent to the dye fixing layer or may be separated through an intermediate layer.
  • the dye fixing layer that is used in the present invention may be composed of two or more layers containing mordants having different mordanting capacities, if necessary.
  • auxiliary layers such as a peeling layer, a matting agent layer, and a curl preventing layer may be provided.
  • a base and/or a base precursor for acceleration of dye transfer an anticorrosion agent for preventing color mixing of hydrophilic heat solvent dyes, a UV absorbing agent, a dispersing vinyl compound, a brightening agent, and other conventional additives may be incorporated.
  • the dye fixing element may include, if necessary, as well as the above layers, a reflection layer containing a white pigment (e.g., titanium oxide), a neutralizing layer, a neutralization timing layer, and so forth. These layers may be coated not only on the dye fixing element but also on the light-sensitive element.
  • the reflection layer, neutralizing layer, and neutralization timing layer are described in, for example, U.S. Pat. Nos. 2,983,606, 3,362,819, 3,362,821, 3,415,644 and Canadian Pat. No. 928,559.
  • the dye fixing element of the present invention may contain a transfer aid as described hereinafter.
  • This transfer aid may be added to the dye fixing layer or another layer.
  • Silver halide which can be used in the light-sensitive element of the present invention includes silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide and silver chloroiodobromide.
  • This silver halide may have a structure in which the halogen composition is uniform throughout the particle, or a multiple structure in which the halogen composition is different between the surface layer and the inside portion, as disclosed in Japanese Patent Application (OPI) Nos. 154232/82, 108533/83, 48755/84 and 52237/84, U.S. Pat. No. 4,433,048, and European Pat. No. 100,984.
  • Two or more silver halides which are different in crystal habit, halogen composition, grain size, grain size distribution, and other properties may be used in combination.
  • Two or more single dispersion emulsions having different grain sizes can be mixed to thereby control gradation.
  • the average grain size is preferably about 0.001 to 10 ⁇ m and more preferably about 0.001 to 5 ⁇ m.
  • These silver halide emulsions may be prepared by any of the acid method, the neutral method, and the ammonia method.
  • a soluble silver salt and a soluble halogen salt can be reacted by any of the single jet method, the double jet method, and a combination thereof.
  • the reverse mixing method in which grains are formed in the presence of an excess of silver ions, and the controlled double jet method in which pAg is kept constant can be employed.
  • the concentration of silver salt or halogen salt added, the amount of silver salt or halogen salt added, or the rate of addition of silver salt or halogen salt may be increased, as disclosed in Japanese Patent Application (OPI) Nos. 142329/80, 158124/80 and U.S. Pat. No. 3,650,757.
  • Silver halide grains of the epitaxial overgrown type can also be used, such as those described in Japanese Patent Application (OPI) No. 16124/81 and U.S. Pat. No. 4,094,684.
  • silver chloroiodide, silver iodobromide, and silver chloroiodobromide in which an X-ray pattern of silver iodide crystal can be observed.
  • silver iodobromide having the above characteristics can be obtained by adding a silver nitrate solution to a potassium bromide solution to thereby prepare silver bromide grains and then further adding potassium iodide thereto.
  • silver halide solvents as silver halide solvents, ammonia, organic thioether derivatives as described in Japanese Patent Publication No. 11386/72, and sulfur-containing compounds as described in Japanese Patent Application (OPI) No. 144319/78 can be used.
  • cadmium salts zinc salts, lead salts, thallium salts, and the like may be present.
  • water-soluble iridium salts such as iridium (III or IV) chloride and hexachloroiridium acid ammonium
  • water-soluble rhodium salts such as rhodium chloride
  • the silver halide emulsion after the formation of precipitate or physical ripening, may be freed of soluble salts.
  • the noodle washing method and the precipitation method can be employed.
  • the silver halide emulsion may primitively be used. Usually, however, it is chemically sensitized. In the case of emulsions for ordinary light-sensitive materials, known sensitizing methods such as sulfur sensitization, reduction sensitization, and noble metal sensitization can be applied alone or in combination with each other. These chemical sensitizations can be carried out in the presence of nitrogen-containing heterocyclic compounds disclosed in Japanese Patent Application (OPI) Nos. 126526/83 and 215644/83.
  • OPI Japanese Patent Application
  • the silver halide emulsion used in the present invention may be of the surface latent image type in which a latent image is formed mainly on the surface of grains, or of the internal latent image type in which a latent image is formed in the interior of the grains.
  • a direct reversal emulsion in which an internal latent image type emulsion and a nucleating agent are used in combination can be used.
  • Internal latent image type emulsions suitable for this purpose are described in, for example, U.S. Pat. Nos. 2,592,250 and 3,761,276, Japanese Patent Publication No. 3534/83, and Japanese Patent Application (OPI) No. 136641/82.
  • Nucleating agents preferably used in combination in the present invention are described in, for example, U.S. Pat. Nos. 3,227,552, 4,245,037, 4,255,511, 4,266,031 and 4,276,364, and German Patent Application (OLS) No. 2,635,316.
  • the amount of light-sensitive silver halide coated is, calculated as silver, from about 1 to 10 g/m 2 .
  • organometallic salts which are relatively stable against light can be used as oxidizing agents in combination with light-sensitive silver halide.
  • organosilver salts are particularly preferred.
  • organometallic salts are used in combination with a light-sensitive silver halide, it is considered that when the heat-developable light-sensitive material is heated at from 80°to 250° C., the organometallic oxidizing agent participates in a redox reaction with the latent image of exposed silver halide as catalyst.
  • Organic compounds which can be used to form the above organosilver salt oxidizing agents include aliphatic or aromatic carboxylic acids, mercapto group-or ⁇ -hydrogen-containing thiocarbonyl group-containing compounds, and imino group-containing compounds.
  • Typical examples of the silver salts of aliphatic carboxylic acids include the silver salts of behenic acid, stearic acid, oleic acid, lauric acid, capric acid, myristic acid, palmitic acid, maleic acid, fumaric acid, tartaric acid, furonic acid, linolic acid, linoleic acid, oleic acid, adipic acid, sebacic acid, succinic acid, acetic acid, butyric acid, and camphoric acid.
  • the silver salts of halogen atom- or hydroxyl group-substituted fatty acids, and thioether group-containing aliphatic carboxylic acids can be used.
  • Typical examples of the silver salts of aromatic carboxylic acids and other carboxyl group-containing compounds include the silver salts of benzoic acid, 3,5-dihydroxybenzoic acid, o-, m- or p-methylbenzoic acid, 2,4-dichlorobenzoic acid, acetamidobenzoic acid, p-phenylbenzoic acid, gallic acid, tannic acid, phthalic acid, terephthalic acid, salicylic acid, phenylacetic acid, pyromellitic acid, and 3-carboxymethyl4-methyl-4-thiazoline-2-thione.
  • Typical examples of the silver salts of mercapto- or thiocarbonyl group-containing compounds include the silver salts of mercapto compounds described in U.S. Pat. No. 4,123,274, such as 3-mercapto-4-phenyl 1,2,4-triazole, 2-mercaptobenzimidazole, 2-mercapto-5-aminothiadiazole, 2-mercaptobenzothiazole, S-alkylthioglycolic acid (wherein the number of carbon atoms in the alkyl group is from about 12 to 22), dithiocarboxylic acids such as dithioacetic acid, thiamides such as thiostearoamide, 5-carboxyl-1-methyl-2-phenyl-4-thiopyridine, mercaptotriazine, 2-mercaptobenzooxazole, mercaptooxadiazole, and 3-amino-5-benzylthio-1,2,4-triazole.
  • Typical examples of the silver salts of imino group-containing compounds include the silver salts of benzotriazole or its derivatives as described in Japanese Patent Publication Nos. 30270/69 and 18416/70, such as benzotriazole, alkyl-substituted benzotriazoles (e.g., methylbenzotriazole), halogen-substituted benzotriazoles (e.g., 5-chlorobenzotriazole), and carboimidobenzotriazoles (e.g., butylcarboimidobenzotriazole), nitrobenzotriazoles as described in Japanese Patent Application (OPI) No.
  • benzotriazole alkyl-substituted benzotriazoles (e.g., methylbenzotriazole), halogen-substituted benzotriazoles (e.g., 5-chlorobenzotriazole), and carboimidobenzotriazoles (e.g., butyl
  • Silver salts and organometallic salts other than the silver salts such as copper stearate, as described in Research Disclosure, 17029 (June, 1978), and the silver salts of alkyl group-containing carboxylic acids such as phenylpropionic acid as described in Japanese Patent Application No. 221535/83 (corresponding to U.S. Patent Application Ser. No. 675,040, filed on Nov. 26, 1984) can be used in the present invention.
  • the amount of the organometallic salt used is typically from about 0.01 to 10 mols, preferably about 0.01 to 1 mol, per mol of light-sensitive silver halide.
  • the total amount of light-sensitive silver halide and organosilver salt being coated is appropriately from about 50 to 10 g/m 2 .
  • the photographic element according to the present invention contains a dye providing substance, i.e., a compound which, when light-sensitive silver halide is reduced into silver under high temperature conditions, forms or releases a mobile dye in a positive or negative relation to the reaction.
  • a dye providing substance i.e., a compound which, when light-sensitive silver halide is reduced into silver under high temperature conditions, forms or releases a mobile dye in a positive or negative relation to the reaction.
  • An example of the dye providing substance which can be used in the present invention is a coupler capable of reacting with a developing agent.
  • the coupler reacts with an oxidized product of the developing agent resulting from the oxidation reduction reaction of the silver salt and the developing agent, thereby forming a dye.
  • This system is well known, and representative examples of the developing agent and coupler are described in detail in, for example, T. H. James, The Theory of the Photographic Process, pp. 291-334 and 354-361 (4th Ed.), and Shinichi Kikuchi, Photographic Chemistry, pp. 284-295 (4th Ed., Kyoritsu Shuppan Co., Ltd.).
  • Dye-silver compounds comprising an organosilver salt and a dye bonded together are also suitable dye providing substances. Representative examples of such dye-silver compounds are described in Research Disclosure, May 1978, pp. 54-58 (RD-16966).
  • Azo dyes conventionally used in the heat-developable silver-dye bleaching method are also useful dye providing substances in the present invention. Representative examples of such azo dyes and a bleaching method are described in U.S. Pat. No. 4,235,957, and Research Disclosure, April 1976, pp. 30-32 (RD-14433).
  • Leuco dyes as described in, for example, U.S. Pat. Nos. 3,985,565 and 4,022,617 are also useful dye providing substances.
  • dye providing substances are compounds having a capability to release or diffuse a diffusible dye in an imagewise pattern represented by the following general formula (LI):
  • Dye is a dye or dye precursor group
  • X 0 is a chemical bonding or connecting group
  • Y 0 is a group which produces a difference in diffusibility between the compound of the general formula: (Dye-X 0 ) n .sbsb.0 Y 0 in a positive or negative relation to a light-sensitive silver salt having an imagewise latent image, or which releases Dye and produces a difference in diffusibility between the released Dye and (Dye-X 0 ) n .sbsb.0 Y 0 ,and n 0 , is 1 or 2, provided that when n 0 is 2, the two Dye-X 0 groups may be the same or different.
  • dye developing agents comprising a hydroquinone-based developing agent and a dye component bonded together are described in U.S. Pat. Nos. 3,134,764, 3,362,819, 3,597,200, 3,544,545 and 3,482,972.
  • Substances releasing a diffusible dye by an intramolecular nucleophilic substitution reaction are described in Japanese Patent Application No. 63618/76, and substances releasing a diffusible dye by an intramolecular rearrangement reaction of an isooxazolone ring are described in Japanese Patent Application (OPI) No. 111628/74.
  • OPI Japanese Patent Application
  • substances releasing a diffusible dye in areas where development occurs substances releasing a diffusible dye by a reaction between a coupler having a diffusible dye as a releasing group and an oxidation product of a developing agent are described in, for example, British Pat. No. 1,330,524, Japanese Patent Publication No. 39165/83, and U.S. Pat. No. 3,443,940, and substances forming a diffusible dye by a reaction between a coupler having a nondiffusing group as a releasing group and an oxidation product of a developing agent are described in, for example, U.S. Pat. No. 3,227,550.
  • dye providing substances which can be used in the present invention are compounds described in Japanese Patent Application (OPI) No. 84236/82, pp. 60-91. Of these compounds, Compounds 1 to 3, 10 to 13, 16 to 19, 28 to 30, 33, 35, 38 to 40, and 42 to 64 are preferred. In addition, the following cyan or yellow dye providing substances are useful. ##STR24##
  • the dye providing substance can be incorporated in a layer of the light-sensitive element by known techniques such as the method described in U.S. Pat. No. 2,322,027. In this case, the following high boiling and low boiling organic solvents can be used.
  • High boiling organic solvents such as phthalic acid alkyl esters (e.g., dibutyl phthalate and dioctyl phthalate), phosphoric acid esters (e.g., diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, and dioctylbutyl phosphate), citric acid esters (e.g., tributyl acetylcitrate), benzoic acid esters (e.g., octyl benzoate), alkylamides (e.g., diethyllaurylamide), fatty acid esters (e.g., dibutoxyethyl succinate and dioctyl azelate), and trimesic acid ester (e.g., tributyl trimesicate), and orgaic solvents having a boiling pint of about 30° to 160° C., such as lower alkyl acetates (e.g.,
  • the dye providing substance is dissolved in an organic solvent described above and then dispersed in a hydrophilic colloid.
  • the above high boiling and low boiling organic solvents may be used in combination with each other.
  • the dispersion method using polymers as described in Japanese Patent Publication No. 39863/76 and Japanese Patent Application (OPI) No. 59943/76 can also be used.
  • various surface active agents can be used.
  • surface active agents those as described hereinafter can be used.
  • the amount of the high boiling organic solvent used is not more than about 10 g, preferably not more than about 5 g, per gram of the dye providing substance.
  • reducing substances compounds generally known as reducing agents and the above described dye providing substances having reducing properties can be used.
  • reducing agent precursors which do not have reducing properties by themselves but exhibit reducing properties in the process of development by the action of nucleophilic reagents or heat can be used.
  • inorganic reducing agents such as sodium sulfite and sodium hydrogensulfite, benzenesulfinic acids, hydroxylamines, hydrazines, hydrazides, boron/amine complexes, hydroquinones, aminophenols, catechols, p-phenylenediamine, 3-pyrazolidinones, hydroxytetronic acid, ascorbic acid, and 4-amino-5-pyrazolones.
  • reducing agents as described in T. H
  • the amount of the reducing agent used is about 0.01 to 20 mols, especially preferably about 0.1 to 10 mols, per mol of silver.
  • an image forming accelerator can be used.
  • the image forming accelerator has various functions such as to accelerate the oxidation reduction reaction between a silver salt oxidizing agent and a reducing agent, to accelerate reactions such as the formation of a dye from a dye providing substance, decomposition of a dye, and release of a mobile dye, ahd to accelerate the transfer of a dye from a layer of the light-sensitive material to a dye fixing layer.
  • such agents can be divided into bases, nucleophilic compounds, oils, heat solvents, surface active agents, compounds having an interaction between silver and silver ions, and so forth. These substances usually have a number of such functions and generally exhibit more than one of the above acceleration effects.
  • image forming accelerators divided into several groups according to their functions are shown below. It is to be noted, however, that this classification is for convenience and in many cases one compound possesses a number of functions.
  • inorganic bases include the hydroxides, di- or triphosphates, borates, carbonates, quinoline acid salts, and metaborates of alkali metals or alkaline earth metals; ammonium hydroxide; hydroxides of quaternary alkylammonium; and hydroxides of other metals.
  • organic bases include aliphatic amines (trialkylamines, hydroxylamines and aliphatic polyamines); aromatic amines (N-alkyl-substituted aromatic amines, N-hydroxyalkyl-substituted aromatic amines, and bis p-(dialkylamino)phenyl methanes), heterocyclic amines, amidines, cyclic amidines, guanidines, and cyclic guanidines. Particularly preferred are those having a pKa of not less than about 8.
  • Examples include water and water releasing compounds, amine compounds, amidine compounds, guanidine compounds, hydroxylamines, hydrazines, hydrazides, oximes, hydroxamic acids, sulfonamides, active methylene compounds, alcohols, and thiols
  • the salts or precursors of the above compounds can be used.
  • High boiling organic solvents as used as solvents in dispersing and emulsifying hydrophobic compounds can be used.
  • Typical examples are pyridinium salts described in Japanese Patent Application (OPI) No. 74547/84, ammonium salts, phosphonium salts, and polyalkylene oxides described in Japanese Patent Application (OPI) No. 57231/84.
  • Typical examples are imides, nitrogen-containing heterocyclic compounds described in Japanese Patent Application No. 51657/83, and thiols, thioureas and thioethers described in Japanese Patent Application No. 222247/82.
  • the image forming accelerator may be incorporated in any one or both of the light-sensitive element and the dye fixing element
  • the image forming accelerator may be incorporated in any of an emulsion layer, an interlayer, a protective layer, a dye fixing layer, and layers adjacent thereto, including materials in which a light-sensitive layer and a dye fixing layer are provided on the same support.
  • the above image forming accelerators can be used alone or in combination with each other. When several types of agents are used in combination, a greater acceleration effect can be obtained.
  • various development stopping agents can be used in combination with the development inhibitor precursors.
  • development stopping agent means a compound which after appropriate development, rapidly neutralizes or reacts with a base, thereby lowering the concentration of the base in the coating layer to stop development, or a compound which inhibits development through the interaction between silver and silver salts.
  • acid precursors releasing an acid on heating electrophilic compounds undergoing a substitution reaction with a base on heating, nitrogen-containing heterocyclic compounds, mercapto compounds, and the like can be listed.
  • acid precursors include oxime esters as described in Japanese Patent Application Nos. 216928/83 and 48305/84, and compounds releasing an acid by the Lossen rearrangement as described in Japanese Patent Application No. 85834/84
  • electrophilic compounds undergoing a substitution reaction with a base on heating are compounds as described in, for example, Japanese Patent Application No. 85836/84.
  • the mol ratio of base precursor to acid precursor is preferably about 1/20 to 20/1 and more preferably about 1/5 to 5/1.
  • compounds for activation of development, and at the same time, for stabilization of an image can be used.
  • Preferred examples of such compounds are compounds having 2-carboxycarboxyamide as an acid portion, such as isothiuroniums (e.g., 2-hydroxyethylisothiuronium trichloroacetate) as described in U.S. Pat. No. 3,301,678, bis(isothiuronium) compounds (e.g., 1,8-(3,6-dioxaoctane)-bis(isothiuronium trichloroacetate) as described in U.S. Pat. No. 3,669,670, thiol compounds described in West German Patent (OLS) No.
  • isothiuroniums e.g., 2-hydroxyethylisothiuronium trichloroacetate
  • bis(isothiuronium) compounds e.g., 1,8-(3,6-dioxaoctane)-
  • thiazolium compounds e.g., 2-amino-2-thiazolium trichloroacetate and 2-amino-5-bromoethyl-2-thiazolium trichloroacetate
  • thiazolium compounds e.g., 2-amino-2-thiazolium trichloroacetate and 2-amino-5-bromoethyl-2-thiazolium trichloroacetate
  • bis(2-amino-2-thiazolium)methylenebis(sulfonylacetate) and 2-amino-2-thiazoliumphenylsulfonyl acetate as described in U.S. Pat. No. 4,060,420.
  • an image toning agent can be incorporated.
  • image toning agents are 1,2,4-triazole, 1H-tetrazole, thiouracil, and 1,3,4-thiadiazole.
  • Preferred toning agent examples include 5-amino-1,3,4-thiadiazole2-thiol, 3-mercapto-1,2,4-triazole, bis(dimethylcarbamyl) disulfide, 6-methylthiouracil and 1-phenyl-2-tetra-azoline-5-thione.
  • Particularly useful toning agents are compounds capable of forming a black image.
  • the concentration of the toning agent varies with the type of the heat-developable light-sensitive element, processing conditions, desired image, and other factors. In general, the concentration of the toning agent is about 0.001 to 0.1 mol per mol of silver contained in the light-sensitive material.
  • Hydrophilic binders can be used. Typical examples of these hydrophilic binders are transparent or translucent hydrophilic binders, including natural substances such as proteins (e.g., gelatin, gelatin derivatives) and polysaccharides (e.g., cellulose derivatives, starch and gum arabic) and synthetic polymeric substances such as water-soluble polyvinyl compounds (e.g., polyvinyl pyrrolidone and polyacrylamide). Other synthetic polymeric substances include vinyl compound dispersions which are used to increase the dimensional stability of the photographic material.
  • proteins e.g., gelatin, gelatin derivatives
  • polysaccharides e.g., cellulose derivatives, starch and gum arabic
  • synthetic polymeric substances such as water-soluble polyvinyl compounds (e.g., polyvinyl pyrrolidone and polyacrylamide).
  • Other synthetic polymeric substances include vinyl compound dispersions which are used to increase the dimensional stability of the photographic material.
  • the amount of the binder coated is not more than about 20 g, preferably not more than about 10 g, and more preferably not more than about 7 g, per square meter.
  • the solvent is used in an amount of about 1 ml or less, preferably about 0.5 ml or less, and more preferably 0.3 ml or less, per gram of the binder.
  • an inorganic or organic hardening agent may be incorporated in a photographic emulsion layer and other binder layers.
  • chromium salts chromium alum and chromium acetate
  • aldehydes e.g., formaldehyde, glyoxal and glutaraldehyde
  • N-methylol compounds e.g., dimethylolurea and methyloldimethylhydantoin
  • dioxane derivatives e.g., 2,3-dihydroxydioxane
  • active vinyl compounds e.g., 1,3,5-triacryloyl-hexahydro-s-triazine, 1,3-vinylsulfonyl-2-propanol and 1,2-bis(vinylsulfonylacetamido)ethane
  • active halogen compounds e.g., 2,4-dichloro-6-hydroxy-s-tria
  • a support capable of standing at a processing temperature is used in the light-sensitive element of the present invention and also in the dye fixing element which is used, if necessary.
  • the support glass, paper, metal and similar materials are used.
  • an acetyl cellulose film, a cellulose ester film, a polyvinyl acetal film, a polystyrene film, a polycarbonate film, a polyethylene terephthalate film, and related films or resinous materials can also be used.
  • a paper support laminated with polymers such as polyethylene ethylene can also be used. Polyesters as described in U.S. Pat. Nos. 3,634,089 and 3,725,070 are preferably used.
  • a dye transfer aid can be used for the transfer of dye from the light-sensitive layer to the dye fixing layer.
  • the transfer aid When the transfer aid is externally applied to the photographic material of the present invention, as the dye transfer aid, water and basic aqueous solutions containing caustic soda, caustic potash, and inorganic alkali metal salts are used. In addition, low boiling solvents such as methanol, N,N-dimethylformamide, acetone, and diisobutyl ketone, and mixtures of such low boiling solvents and water or basic aqueous solutions can be used.
  • the dye transfer aid can be used according to a method in which the image receiving layer is wetted with the transfer aid.
  • the transfer aid is incorporated in the light-sensitive element or dye fixing element, it is not necessary to supply the transfer aid externally.
  • the transfer aid may be incorporated in the material in the form of water of crystallization or of microcapsules, or as a precursor releasing a solvent at a high temperature.
  • a more preferred method is to incorporate a hydrophilic heat solvent which is solid at ordinary temperature and melts at an elevated temperature in the light-sensitive element or dye fixing element.
  • a hydrophilic heat solvent may be incorporated in any one or both of the light-sensitive element and the dye fixing element
  • the hydrophilic heat solvent may be incorporated in any of an emulsion layer, an interlayer, protective layer, and a dye fixing layer. It is preferred, however, that the hydrophilic heat solvent be incorporated in the dye fixing layer and/or its adjacent layers.
  • hydrophilic heat solvents examples include ureas, pyridines, amides, sulfonamides, imides, alcohols, oximes, and other heterocyclic compounds.
  • a dye providing substance of the above general formula (LI) is incorporated in the light-sensitive element of the present invention, since the dye providing substance is colored, it is not necessary to further incorporate an anti-irradiation or antihalation substance or various dyestuffs in the light-sensitive element, but in order to improve the sharpness of images, filter dyestuffs, absorbing substances, and the like as described in Japanese Patent Publication No. 3692/73, U.S. Pat. Nos. 3,253,921, 2,527,583 and 2,956,879 can be added. As such dyestuffs, those undergoing decoloration on heating are preferred. For example, dyestuffs as described in U.S. Pat. Nos. 3,769,019, 3,745,009 and 3,615,432 are preferred.
  • the light-sensitive element which is used in the present invention may contain, if necessary, various conventional additives used in heat-developable light-sensitive materials, such as a plasticizer, a sharpness improving dyestuffs, an AH dyestuff (i.e., antihalation dyestuff), a sensitizing dye, a matting agent, a surface active agent, a brightening agent, and an antifading agent as described in Research Disclosure, Vol. 170, June, 1978, No. 17029.
  • a plasticizer such as a plasticizer, a sharpness improving dyestuffs, an AH dyestuff (i.e., antihalation dyestuff), a sensitizing dye, a matting agent, a surface active agent, a brightening agent, and an antifading agent as described in Research Disclosure, Vol. 170, June, 1978, No. 17029.
  • a mordant used in the dye fixing layer in the present invention can be selected appropriately from commonly used mordants.
  • polymer mordants are particularly preferred.
  • These polymer mordants include polymers containing a tert-amino group, polymers containing a nitrogen-containing heterocyclic portion, and polymers containing these quaternary cationic groups.
  • polymers containing a vinyl monomer unit having a tert-amino group are described in, for example, Japanese Patent Application Nos. 169012/83 and 166135/83.
  • polymers containing a vinyl monomer unit having a tert-imidazole group are described in Japanese Patent Application Nos. 226497/83, 232071/83, U.S. Pat. Nos. 4,282,305, 4,115,124 and 3,148,061.
  • Preferred examples of polymers containing a vinyl monomer unit having a quaternary imidazolium salt are described in, for example, British Pat. Nos. 2,056,101, 2,093,041, 1,594,961, U.S. Pat. Nos. 4,124,386, 4,115,124, 4,273,853, 4,450,224 and Japanese Patent Application (OPI) No. 28225/83.
  • polymers containing a vinyl monomer unit having a quaternary ammonium salt are described in, for example, U.S. Pat. Nos. 3,709,690, 3,898,088, 3,958,995, Japanese Patent Application Nos. 166135/83, 169012/83, 232070/83, 232072/83 and 91620/84.
  • a light source for imagewise exposure of the heat-developable light-sensitive material radiation including visible light can be used.
  • light sources commonly used for color printing such as a tungsten lamp, a mercury lamp, a halogen lamp (e.g., an iodine lamp), a xenon lamp, a laser light source, a CRT light source, a fluorescent tube, a light emitting diode (LED) and the like can be employed.
  • the heating temperature for heat development is from about 80° to 250° C.
  • a useful heating temperature is between about 110° and 180° C. Within this temperature range, temperatures of at least 140° C. are preferred, and temperatures of at least 150° C. are particularly preferred.
  • the transfer process can be carried out within a temperature range between approximately the heating temperature for heat development and room temperature. A temperature range between about the heating temperature for heat development and a temperature about 10° C. lower than the heating temperature for heat development is more preferred.
  • a heating means for heat development and transfer a hot plate, an iron, a heat roller, and heat generators using carbon or titanium white, for example, can be used.
  • the dye transfer aid e.g., water
  • the dye transfer aid can be introduced between a light-sensitive layer of the heat-developable light-sensitive element and a dye fixing layer of the dye fixing material to accelerate the transfer of images. It is also possible to apply the dye transfer aid to any one or both of the light-sensitive layer and the dye fixing layer, and then to superpose the light-sensitive layer and the dye fixing layer.
  • the dye transfer aid can be added to the light-sensitive layer or dye fixing layer by techniques such as the roller coating method or wire bar coating method described in Japanese Patent Application (OPI) No. 55907/83, the method of coating water on the dye fixing material using a water absorbing material as described in Japanese Patent Application No. 55908/73, the method of adding the dye transfer aid by forming beads between the heat-developable light-sensitive element and the dye fixing element as described in Japanese Patent Application No. 55906/83, the method of adding the dye transfer aid by forming beads between a water repellent roller and the dye fixing layer as described in Japanese Patent Application No. 55910/83, the dipping method, the extrusion method, the method of adding the dye transfer aid by jetting it through small holes, and the method of adding the dye transfer aid by rupturing a pod containing the agent.
  • the dye transfer aid may be supplied in a predetermined amount as described in Japanese Patent Application No. 37902/83, or may be supplied in a sufficient amount, and then squeezed off by applying pressure using a roller, for example, and dried by heating to thereby control the amount thereof.
  • One typical method is to apply the dye transfer aid to the dye fixing element by the above described method, pass the dye fixing element through rollers under pressure to remove an excess of the dye transfer aid, and then superpose the dye fixing element on the heat-developable light-sensitive material.
  • heating can be carried out by various techniques such as heating by passing between hot plates, heating by bringing the element into contact with a hot plate (see, for example, Japanese Patent Application (OPI) No. 62635/75), heating by bringing the element into contact with a rotary hot drum or hot roll (see, for example, Japanese Patent Publication No. 10791/78), heating by passing the element through a hot air (see, for example, Japanese Patent Application (OPI) No. 32737/78), heating by passing the element through an inert liquid maintained at a given temperature, and heating by moving the element along a heat source by means of a roller, a belt or a guide member (see, for example, Japanese Patent Publication No. 2546/69).
  • a method can be employed in which the dye fixing material is provided with a layer of an electrically conductive material such as graphite, carbon black and metal and is directly heated by passing an electric current through the electrically conductive layer.
  • the dye transfer can be attained by heating at a temperature ranging from the heat development temperature to room temperature. It is particularly preferred that the element be heated at a temperature not less than about 60° C. and at least about 10° C. lower than the temperature at the heat development step.
  • the pressure under which the heat-developable light-sensitive material and the dye fixing element are brought into close contact with each other varies depending on a method of superposing the elements and the type of each element.
  • the pressure is from about 0.1 to 100 kg/cm 2 and preferably from about 1 to 50 kg/cm 2 (as described in, for example, Japanese Patent Application No. 55691/83).
  • the heat-developable light-sensitive material and the dye fixing element can be pressed by techniques such as by passing the elements between a pair of rollers, or by pressing the elements on a plate having high smoothness.
  • the roller or plate when pressure is applied, may be heated at a temperature ranging from room temperature to the temperature at the heat development step.
  • the silver iodobromide emulsion thus obtained was precipitated to remove an excess of salts. Then, the emulsion was adjusted to pH 6.0 to yield 400 g of a silver iodobromide emulsion.
  • This silver benzotriazole emulsion was precipitated to remove an excess of salts. Then, it was adjusted to pH 6.0 to yield 400 g of a silver benzotriazole emulsion.
  • Compound (37) of the present invention (3 g) was added to 100 g of a 1 wt % aqueous gelatin solution and ground for 10 minutes in a mill using 100 g of glass beads having an average particle size of about 0.6 mm. The glass beads were separated by filtration to obtain a gelatin dispersion of the compound of the present invention.
  • the above ingredients were mixed, dissolved by heating, coated on a 180 ⁇ m thick polyethylene terephthalate film in a wet coating thickness of 33 ⁇ m, and then dried. Moreover, as a protective layer, the following composition was coated thereon.
  • Light-Sensitive Elements A and B were each exposed imagewise at 2,000 lux for 10 seconds using a tungsten lamp and then uniformly heated for 30 seconds on a heat block maintained at 140° or 143° C.
  • the dye fixing element was dipped in water. Then, the heated Light-Sensitive Elements A and B were each superposed on the dye fixing element such that the coatings of the elements were in contact with each other.
  • the light-sensitive and dye fixing elements were heated for 6 seconds on a heat block maintained at 80° C. and then the dye fixing element was peeled apart from the light-sensitive element whereupon a negative magenta dye was formed on the dye fixing element.
  • This negative image was measured for density by the use of a Macbeth reflection densitometer (RD-519). The results are shown in Table 1.
  • a multilayer color photographic element was prepared as follows.
  • a mixture of 5 g of Yellow Dye Providing Substance (2), 0.5 g of sodium 2-ethylhexylsuccinate sulfonate as a surface active agent, and 10 g of triisononyl phosphate was dissolved in 30 ml of ethyl acetate by heating at about 60° C. to prepare a uniform solution.
  • This solution was mixed with 100 g of a 10 wt % solution of lime-processed gelatin, and then dispersed therein at 10,000 rpm for 10 minutes using a homogenizer, to obtain a "dispersion of the yellow dye providing substance".
  • a dispersion of a magenta dye providing substance was prepared in the same manner as above except that Magenta Dye Providing Substance (1) used in Example 1 was used. Also, a dispersion of Cyan Dye Providing Substance (3) shown below was prepared in the same manner as above.
  • the above multilayer color light-sensitive element was exposed through Blue, Green and Red three color separation filters continuously changing in density at 2,000 lux for 10 seconds using a tungsten lamp.
  • aqueous gelatin solution prepared by dissolving 20 g of gelatin and ammonia in 1,000 ml of water and maintained at 50° C.
  • an aqueous gelatin solution prepared by dissolving 20 g of gelatin and ammonia in 1,000 ml of water and maintained at 50° C.
  • an aqueous silver nitrate solution prepared by dissolving 1 mol of silver nitrate in 1,000 ml of water.
  • aqueous gelatin solution prepared by dissolving 20 g of gelatin and 3 g of sodium chloride in 1,000 ml of water and maintained at 75° C.
  • an aqueous silver nitrate solution prepared by dissolving 0.59 mol of silver nitrate in 600 ml of water
  • Dye (I) solution as described hereinafter all at the same time at an equal flow rate over 40 minutes.
  • a single dispersion cubic silver chlorobromide emulsion bromine: 80 mol %) having an average particle size of 0.35 ⁇ m, with the dye adsorbed thereon was prepared.
  • aqueous gelatin solution prepared by dissolving 20 g of gelatin and 3 g of sodium chloride in 1,000 ml of water and maintained at 75° C.
  • an aqueous gelatin solution prepared by dissolving 20 g of gelatin and 3 g of sodium chloride in 1,000 ml of water and maintained at 75° C.
  • 600 ml of an aqueous solution containing sodium chloride and potassium bromide and an aqueous silver nitrate solution prepared by dissolving 0.59 mol of silver nitrate in 600 ml of water
  • a single dispersion cubic silver chlorobromide emulsion (bromine: 80 mol %) having an average particle size of 0.35 ⁇ m was prepared.
  • the silver benzotriazole emulsion was prepared in the same manner as in Example 1.
  • the above multilayer color light-sensitive element was exposed through B, G and R three color separation filters continuously changing in density at 2,000 lux for 1 second by the use of a tungsten lamp. Then, the element was uniformly heated for 30 seconds on a heat block maintained at 140° C.
  • the light-sensitive element thus prepared was superposed on the dye fixing element in such a manner that the coatings were in contact with each other.
  • This light-sensitive element/dye fixing element assembly was passed through a heat roll maintained at 130° C. under pressure and then immediately heated on a heat block at 120° C. for 30 seconds.
  • the dye fixing element was peeled apart from the light-sensitive element whereupon yellow, magenta and cyan dye images were formed on the dye fixing element according to the B, G and R three color separation filters. Each color was measured for the maximum and minimum densities by the use of a Macbeth reflection densitometer (RD-519). The results are shown in Table 4.
  • a dispersion of a reducible dye providing substance was prepared in the same manner as in Example 5 except that a mixture of 5 g of Dye Providing Substance (5) having the formula shown below, 4 g of electron doner shown below, 0.5 g of sodium 2-ethylhexylsuccinate sulfonate, and 10 g of tricresyl phosphate was dissolved in 20 ml of cyclohexanone by heating at about 60° C. ##
  • Light-Sensitive Element M was prepared in the same manner as in the preparation of Light-Sensitive Element L of Example 5 except that a dispersion of the above reducible dye providing substance was used in place of the dispersion of Dye Providing Substance (4). And the same dye fixing element as in Example 1 was used as a dye fixing element.
  • a mixture of 5 g of 2-dodecylcarbamoyl-1-naphthol, 0.5 g of sodium 2-ethylhexylsuccinate sulfonate, and 2.5 g of tricresyl phosphate (TCP) was dissolved in 30 ml of ethyl acetate.
  • the resulting solution was mixed with 100 g of a 10 wt % solution of gelatin and then dispersed therein at 10,000 rpm for 10 minutes by the use of a homogenizer.
  • This Light-Sensitive Element N was exposed imagewise at 2,000 lux for 5 seconds by the use of a lamp. Then, Element N was uniformly heated on a heat block maintained at 150° C. or 153° C. for 20 seconds, whereupon a negative cyan image was formed. The image was measured for the density by the use of a Macbeth transmission densitometer (TD-504). The results are shown in Table 7.
  • a black-and-white material is described in example.
  • the above ingredients were mixed to prepare a coating solution, and this coating solution was coated on a polyethylene terephthalate support in a wet coating thickness of 60 ⁇ m and then dried.
  • the light-sensitive element thus obtained was exposed imagewise at 2,000 lux for 5 seconds by the use of a tungsten lamp. Then, the element was uniformly heated on a heat block maintained at 130° C. or 133° C. for seconds, whereupon a negative brown image was obtained. The image was measured for the density by the use of a Macbeth transmission densitometer (TD-504). The results are shown in Table 8.

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US07/153,535 1984-12-20 1988-02-01 Heat developable photographic element Abandoned USH691H (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP59268926A JPH067253B2 (ja) 1984-12-20 1984-12-20 熱現像写真要素
JP59-268926 1984-12-20

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US06809627 Continuation 1985-12-16

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US07/153,535 Abandoned USH691H (en) 1984-12-20 1988-02-01 Heat developable photographic element

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EP0559101A1 (en) * 1992-03-02 1993-09-08 Canon Kabushiki Kaisha Heat-developable photosensitive material and image forming method which uses the same

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JPS63153539A (ja) * 1986-08-08 1988-06-25 Konica Corp 新規な抑制剤を含有し、保存性の優れた熱現像感光材料
CA1298415C (en) * 1987-01-13 1992-03-31 Makoto Ohgoda Radiation image read-out and reproducing apparatus
JP2587960B2 (ja) * 1987-01-13 1997-03-05 富士写真フイルム株式会社 放射線画像情報記録読取再生装置
JP2519920B2 (ja) * 1987-04-08 1996-07-31 富士写真フイルム株式会社 画像形成方法
JPH01167750A (ja) * 1987-12-23 1989-07-03 Konica Corp 熱現像感光材料
JP2597908B2 (ja) 1989-04-25 1997-04-09 富士写真フイルム株式会社 ハロゲン化銀カラー写真感光材料
EP0502508B1 (en) 1991-03-05 1999-07-07 Fuji Photo Film Co., Ltd. Diffusion transfer color photographic material and heat-developable color photographic material
JP3078153B2 (ja) * 1993-07-08 2000-08-21 富士写真フイルム株式会社 感光性組成物

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EP0559101A1 (en) * 1992-03-02 1993-09-08 Canon Kabushiki Kaisha Heat-developable photosensitive material and image forming method which uses the same

Also Published As

Publication number Publication date
JPH067253B2 (ja) 1994-01-26
JPS61147244A (ja) 1986-07-04

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