EP0357040A1 - Wärmeentwickelbares photographisches Farbmaterial und Bildherstellungsverfahren damit - Google Patents

Wärmeentwickelbares photographisches Farbmaterial und Bildherstellungsverfahren damit Download PDF

Info

Publication number
EP0357040A1
EP0357040A1 EP89116013A EP89116013A EP0357040A1 EP 0357040 A1 EP0357040 A1 EP 0357040A1 EP 89116013 A EP89116013 A EP 89116013A EP 89116013 A EP89116013 A EP 89116013A EP 0357040 A1 EP0357040 A1 EP 0357040A1
Authority
EP
European Patent Office
Prior art keywords
group
dye
formula
heat
photographic material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP89116013A
Other languages
English (en)
French (fr)
Other versions
EP0357040B1 (de
Inventor
Hiroyuki C/O Fuji Photo Film Co. Ltd. Hirai
Nobutaka C/O Fuji Photo Film Co. Ltd. Ohki
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujifilm Holdings Corp
Original Assignee
Fuji Photo Film Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fuji Photo Film Co Ltd filed Critical Fuji Photo Film Co Ltd
Publication of EP0357040A1 publication Critical patent/EP0357040A1/de
Application granted granted Critical
Publication of EP0357040B1 publication Critical patent/EP0357040B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
    • G03C8/40—Development by heat ; Photo-thermographic processes
    • G03C8/4013—Development by heat ; Photo-thermographic processes using photothermographic silver salt systems, e.g. dry silver
    • G03C8/408—Additives or processing agents not provided for in groups G03C8/402 - G03C8/4046

Definitions

  • the present invention relates to a heat-­developable photographic material and to a method for forming an image using the same.
  • the heat-developable photographic materials to be used in the said methods for forming color images are of a non-fixable type
  • the silver halide would still remain in the material even after formation of images. Accordingly, such materials have a serious problem that the white portion in the material is gradually colored after it has been exposed to a strong light or has been stored for a long period of time.
  • the known methods generally require a relatively long period of time for development, and these have an additional drawback that the image formed is noticeably fogged and has a low image density.
  • the amount of the binder in the interlayer is less than that in the conventional wet-type photographic material in view of the image-forming speed, the diffusive dye-­transferring speed and the resolving power, and accordingly, it is also desired that the reducing compound to be added to the interlayer is one capable of displaying high effect even when used in a small amount.
  • An object of the present invention is to provide a heat-developable color photographic material which has an excellent color reproducibility and which may form an image with high image density and low stain.
  • Another object of the present invention is to provide a heat-developable color photographic material which is thin and which has an improved sharpness.
  • a heat-developable color photographic material comprising a support having thereon a light-­sensitive silver halide, a binder, a diffusive reducing agent and a dye donor compound capable of releasing or forming a diffusive dye in correspondence or reverse correspondence with the reaction of reducing the silver ion into silver, wherein the material comprises at least two light-sensitive layers each having a different color sensitivity and at least one layer containing at least one compound represented by the following formula (I) between the two light-sensitive layers, and by a method of forming a color image by heat-developing the material after simultaneously with imagewise exposure thereof or simultaneously with imagewise exposure thereof.
  • R1 and R2 each represents a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkyl, acylamino, alkoxy, aryloxy, alkylthio, arylthio, sulfonyl, acyl, carbamoyl or sulfamoyl group; or R1 and R2 may together form a carbon ring;
  • X represents -CO- or -SO2-;
  • R3 represents a substituted or unsubstituted alkyl, aryl, heterocyclic, alkoxy, aryloxy or amino group; provided that the total of the carbon atoms in R1, R2, and R3 is 10 or more, and the compound of the formula (I) is substantially insoluble in water.
  • R1 and R2 in the formula (I) each represents a hydrogen atom, a halogen atom (e.g., chlorine, bromine), a substituted or unsubstituted alkyl group (preferably having from 1 to 60 carbon atoms e.g., methyl, pentadecyl, t-hexyl), a substituted or unsubstituted acylamino group (preferably having from 2 to 60 carbon atoms e.g., acetylamino, benzoylamino), a substituted or unsubstituted alkoxy group (preferably having from 1 to 60 carbon atoms e.g., methoxy, butoxy), a substituted or unsubstituted aryloxy group (preferably having from 6 to 60 carbon atoms e.g., phenoxy), a substituted or unsubstituted alkylthio group (preferably having from 1 to 60 carbon atoms e.g., octy
  • R1 and R2 may together form a carbon ring, preferably a 5- to 7-membered carbon ring.
  • X represents -CO- or -SO2-.
  • R3 represents a substituted or unsubstituted alkyl group (preferably having from 1 to 60 carbon atoms e.g., heptadecyl, 1-hexylnonyl, 1-(2,4-­ di-t-amylphenoxy)propyl; additionally, a substituted or unsubstituted cycloalkyl group such as 3-decanamido­cyclohexyl or 2- ⁇ (2,4-di-t-amylphenoxy)butanamido ⁇ cyclo­hexyl group is also preferred), a substituted or unsubstituted aryl group (preferably having from 6 to 60 carbon atoms e.g., phenyl, 3,5-bis(2-hexyl­decanamido)phenyl, 3,4-bis(he
  • the total of the carbon atoms in R1, R2, and R3 is 10 or more, and the compound of the formula (I) is substantially insoluble in water.
  • the solubility in water of the compound of the formula (I) is 0.1 g/l or less.
  • R1 to R3 in the formula (I) may have further substituents.
  • substituents there are mentioned generally known organic groups (e.g., alkyl, alkoxy, alkylthio, acylamino, alkloxycarbonyl), halogen atoms and a hydroxyl group, but the compound does not contain a sulfo group and a carboxyl group as the substituent.
  • the compound of the formula (I) for use in the present invention does not have sulfo group and carboxyl group as the substituent and the compound is substantially insoluble in water.
  • the compound of the formula (I) may form a bis-­form, a tris-form or a polymer.
  • R1 and R2 in the formula (I) each represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or an alkylthio group; and most preferably they each represents a hydrogen atom, a halogen atom or an alkyl group.
  • X is preferably -CO-.
  • R3 is preferably an alkyl group or an aryl group, most preferably it is an aryl group.
  • R3 in the formula (I) represents an aryl group
  • the substituents on the group are not specifically limitative, provided that they are generally known substituents substitutable on an aryl ring.
  • substituents there are mentioned a halogen atom, an alkyl group, an amido group, a sulfonamido group, an alkoxy group, an alkoxycarbonyl group and a carbamoyl group.
  • the total of the carbon atoms in R1, R2 and R3 is preferably from 10 to 60, more preferably from 15 to 50.
  • the compounds of the formula (I) can be prepared by the methods described in JP-B-59-37497 (the term "JP-­B” as used herein means an "examined Japanese patent publication") and JP-A-62-103053 and in accordance with the methods.
  • the compound of the formula (I) is added to a non-light-sensitive layer (interlayer) to be provided between two silver halide emulsion layers each having a different color sensitivity.
  • the compound may further be added to any other non-light-sensitive layer (protective layer) or emulsion layer.
  • the same compound may be added to two or more different layers, or two or more different kinds of the compounds of the formula (I) may be added to one and the same layer.
  • the interlayer containing the compound of the formula (I) may have a function as yellow filter layer.
  • the amount of the compound of the formula (I) to be added is preferably from 1 ⁇ 10 ⁇ 6 to 1 ⁇ 10 ⁇ 2 mol/m2, and more preferably from 10 ⁇ 5 to 2 ⁇ 10 ⁇ 3 mol/m2.
  • the compound of the formula (I) may be incorporated into the photographic material by various known dispersion methods.
  • a solid dispersion method an alkali dispersion method, preferably a latex dispersion method, more preferably an oil-in-water dispersion method.
  • the compound is first dissolved in a single solvent which is a high boiling point organic solvent having a boiling point of 175°C or higher or a so-called auxiliary solvent having a low boiling point or in a mixed solvent of the two and then the resulting solution is finely dispersed in an aqueous medium such as water or an aqueous gelatin solution in the presence of a surfactant.
  • the dispersion may be accompanied by phase conversion. If desired, the auxiliary solvent used may be removed or reduced by distillation, noodle washing or ultrafiltration before coating the dispersion.
  • phthalic acid esters e.g., dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, didodecyl phthalate
  • phos­phoric acid or phosphonic acid esters e.g., triphenyl phosphate, tricresyl phosphate, 2-ethylhexyldiphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phos­phate, trichloropropyl phosphate, di-2-ethylhexylphenyl phosphate), benzoic acid esters (e.g., 2-ethylhexyl benzoate, dodecyl benzoate, 2-ethylhexyl p-­
  • auxiliary solvent that having a boiling point of from about 30°C to about 160°C is employed.
  • auxiliary solvent that having a boiling point of from about 30°C to about 160°C.
  • Specific examples of such solvent include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-­ethoxyethyl acetate and dimethylformamide.
  • a latex dispersion method may be applied to dispersion of the compound of the formula (I) of the invention, and the procedure and effect of the process as well as latexes usable in the process are described in U.S. Patent No. 2,541,274 and West German Patent OLS No. 2,541,230.
  • At least three silver halide emulsion layers each having a different light-sensitivity in a different spectral range are combined. For instance, there are mentioned a combination of three layers of a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer and a combination of three layers of a green-sensitive layer, a red-sensitive layer and an infrared-sensitive layer.
  • the light-sensitive layers may be positioned in various sequences known for conventional color photographic materials.
  • the light-sensitive layer may be composed of two or more layers having the same color-sensitivity but each having a different sensitivity degree.
  • the heat-developing photographic material of the present invention may have, in addition to the interlayer containing the compound of the formula (I) of the invention to be provided between two light-sensitive layers each having a different color-sensitivity, various auxiliary layers such as protective layer, subbing layer, yellow filter layer, antihalation layer and backing layer.
  • the silver halide which is employable in the present invention may be any of silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodide and silver chloroiodobromide.
  • the silver halide emulsion for use in the present invention may be either a surface latent image-­type emulsion or an internal latent image-type emulsion.
  • the internal latent image-type emulsion is used as a direct reversal emulsion in combination with a nucleat­ing agent or with light-fogging.
  • the emulsion may be a so-called core/shell emulsion having different phases in the inside of the grain (core) and the surface layer thereof (shell).
  • the silver halide emulsion may be either monodispersed or polydispersed, and plural monodispersed emulsions can be used in combination.
  • the grain size of the emulsion grains is preferably from 0.1 to 2 ⁇ m, especially from 0.2 to 1.5 pm.
  • the grains may be any of cubic, octahedral or tetradecahedral grains or tabular grains with high aspect ratio or others.
  • the silver halide emulsions can be used in the form not after-ripened, these are generally used after being chemically sensitized.
  • any of sulfur sensitization method, reduction sensitization method and noble metal sensitization method which are known for emulsions of conventional photographic materials can be employed singly or in combination.
  • Such chemical sensitization can be effected in the presence of a nitrogen-containing heterocyclic compound (as described in JP-A-62-253159).
  • the amount of the light-sensitive silver halide to be coated on the support for forming the photographic material of the present invention is form 1 mg/m2 to 10 g/m2 as silver.
  • an organic metal salt is employed as an oxidizing dye, together with the light-sensitive silver halide.
  • organic silver salts are especially preferably used.
  • organic compound employable for forming the said organic silver salt oxidizing agent there are mentioned benzotriazoles, fatty acids and other compounds described in U.S. Patent 4,500,626, columns 52 to 53.
  • silver salts of alkynyl group-­containing carboxylic acids such as silver phenyl­propiolate, described in JP-A-60-113235, as well as silver acetylene described in JP-A-61-249044 are also usable. Two or more kinds of such organic silver salts can be employed in combination.
  • the organic silver salt can be incorporated into the photographic material in an amount of from 0.01 to 10 mols, preferably from 0.01 to 1 mol, per mol of the light-sensitive silver halide.
  • the total of the light-­sensitive silver halide and the organic silver salt is suitably from 50 mg/m2 to 10 g/m2 as silver.
  • various antifoggants and photographic stabilizers can be employed.
  • the agents there are mentioned azoles and azaindenes described in RD Item No. 17643 (1978), pages 24 to 25; nitrogen-containing carboxylic acids and phosphoric acids described in JP-A-­59-168442; mercapto compounds and metal salts thereof described in JP-A-59-111636; and acetylene compounds described in JP-A-62-87957.
  • the silver halides for use in the present invention can be color-sensitized with methine dyes or the like.
  • Dyes usable for the purpose include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonole dyes.
  • the sensitizing dyes can be used singly or in combination. Combination of sensitizing dyes is often employed for the purpose of supersensitization.
  • the emulsions for use in the present invention can contain dyes which do not have color-sensitizing action by themselves or compounds which do not substantially absorb visible lights but have supersensitizing action, together with the sensitizing dyes. (For instance, such dyes or compounds are described in U.S. Patent 3,615,641 and JP-A-63-23145).
  • the sensitizing dyes can be added to the emulsions at any time of during chemical ripening of the emulsion or before or after chemical ripening thereof. Further, they may also be added before or after formation of nuclei of silver halide grains, in accordance with U.S. Patents 4,183,756 and 4,225,666.
  • the amount of the dye to be added to the emulsion is generally about from 10 ⁇ 8 to 10 ⁇ 2 mol per mol of silver halide.
  • hydrophilic substances are preferably employed.
  • the substances described in JP-A-62-­253159, pages 26 to 28 are referred to.
  • transparent or semi-transparent binders are preferred, and for example, there are mentioned natural compounds including proteins such as gelatin and gelatin derivatives as well s polysaccharides such as cellulose derivatives, starch, gum arabic, dextran and pullulane; and synthetic high polymer compounds such as polyvinyl alcohol, polyvinyl pyrrolidone, acrylamide polymer and others.
  • the high water-absorbing polymers described in JP-A-62-245260 can also be used, which are homopolymers of vinyl monomers having -COOM or -SO3M (where M means a hydrogen atom or an alkali metal atom) or copolymers of the said vinyl monomers or of the said vinyl monomer(s) and other vinyl monomer(s) (e.g., sodium methacrylate, ammonium methacrylate, Sumicagel L-­5H manufactured by Sumitomo Chemical Co.). Two or more kinds of such binders can be used in combination.
  • the photographic material is desired to contain the said high water-absorbing polymer whereby absorption of water may be effected rapidly. It is also preferred to incorporate the said high water-­absorbing polymer into the dye-fixing layer and the protective layer therefor, whereby re-transferring of the once transferred dye to any other material from the dye-fixing material may be prevented.
  • the amount of the binder to be coated is preferably 20 g or less, especially 10 g or less, more preferably 7 g or less, per m2 of the photographic material.
  • the layers (including backing layer) constitut­ing the light-sensitive photographic materials and the dye-fixing materials of the present invention can contain various polymer latexes for the purpose of improving the film property of the material, for example, for the purpose of dimension stabilization, curling prevention, blocking prevention, film cracking prevention and prevention of pressure sensitization and desensitization (pressure marks).
  • polymer latexes described in JP-A-62-245258, JP-­A-62-136648 and JP-A-62-110066 can be employed for such a purpose.
  • the photographic material of the present invention contains a compound which can form or release a diffusive dye in correspondence or reverse corres­pondence with the reaction of reducing silver ion into silver under high temperature condition, or a dye donor compound.
  • the dye donor compounds to be employed in the present invention there are mentioned compounds (couplers) capable of forming a dye by oxidation-coupling reaction.
  • the coupler may be either 4-equivalent or 2-equivalent.
  • 2-Equivalent couplers which have a non-diffusive group as the releasing group and which form a diffusive dye by oxidation-coupling reaction are also preferred.
  • the non-diffusive group may be in the form of a polymer chain. Examples of such dye-forming couplers are described in detail in T.H.
  • a further example of the dye donor compound includes a compound adapted to imagewise release or spread of a diffusive dye.
  • Compounds of such type can be represented by formula (LI) (Dye-Y) n -Z (LI) wherein Dye represents a dye group or a dye precursor group whose absorption wavelength has been shortened temporarily; Y represents a chemical bond or a lining group; and Z represents a group which either causes an imagewise differential in the diffusibility of the compound (Dye-Y) n -Z in correspondence or reverse correspondence with the photosensitive silver salt carrying a latent image or releases the Dye and causes a differential in diffusibility between the released Dye and (Dye-Y) n -Z; n represents 1 or 2 and when n is 2, the two Dye-Y groups may be the same or different.
  • the compounds (1) through (3) are those of forming a diffusive color image in reverse correspondence with development of silver halide (positive color image) ; and the compounds (4) and (5) are those of forming a diffusive color image in correspondence with development of silver halide (negative color image).
  • Color-developing agents comprising a combination of a hydroquinone developing agent and a dye component, described in U.S. Patents 2,134,764, 3,362,819, 3,597,200, 3,544,545 and 3,482,972.
  • the color-developing agents are diffusive under an alkaline condition but become non-diffusive after reacted with a silver halide.
  • Non-diffusive compounds which may release a diffusive dye under an alkaline condition but which lose their capacity when reacted with a silver halide can also be used, as so described in U.S. Patent 4,503,137.
  • examples of such compounds there are mentioned the compounds of releasing a diffusive dye by intramolecular nucleophilic substitution reaction described in U.S. Patent 3,980,479 and the compounds of releasing a diffusive dye by intramolecular rearrangement reaction of the isoxazolone ring described in U.S. Patent 4,199,354.
  • Non-diffusive compounds capable of reacting with a reducing agent which had remained without being oxidized by development to release a diffusive dye can also be used, as so described in U.S. Patent 4,559,290, European Patent 220,746A2 and Kokai Giho (Disclosure Bulletin) 87-6199.
  • Patents 4,343,893 and 4,619,887 the nitro compounds of releasing a diffusive dye after electron reception described in U.S. Patent 4,450,223; and the compounds of releasing a diffusive dye after electron reception described in U.S. Patent 4,609,610.
  • the compounds having an N-X bond (where X means an oxygen sulfur or nitrogen atom) and an electron-attracting group in one molecule described in European Patent 220,746A2, Kokai Giho (Disclosure Bulletin) 87-6199, JP-­A-63-201653 and JP-A-63-201654; the compounds having SO2-X (where X has the same meaning as mentioned above) and an electron-attracting group in one molecule described in JP-A-1-26842; the compounds having a PO-X bond (where X has the same meaning as mentioned above) and an electron-attracting group in one molecule described in JP-A-63-271344; the compounds having a C-­X′ bond (where X′ has the same meaning as mentioned above or means -SO2-) and an electron-attracting group in one molecule described in JP-A-63-271341; and the compounds of releasing a photographically useful group by cleavage of the single bond, after reduced, by the ⁇ -­
  • the compounds having an N-X bond and an electron-attracting group in one molecule includes Compounds (1) to (3), (7) to (10), (12), (13), (15), (23) to (26), (31), (32), (35), (36), (40), (41), (44), (53) to (59), (64) and (70) described in European Patent 220,746A2 and Compounds (11) to (23) described in Kokai Giho (Disclosure Bulletin) 87-6199.
  • DDR couplers which have a diffusive dye as the releasing and release the diffusive dye by reaction with the oxidation product of a reducing agent are also used.
  • DDR couplers which have a diffusive dye as the releasing and release the diffusive dye by reaction with the oxidation product of a reducing agent are also used.
  • DDR couplers which have a diffusive dye as the releasing and release the diffusive dye by reaction with the oxidation product of a reducing agent.
  • DRR compounds which have a property of reducing silver halides and organic silver salts and which release a diffusive dye after having reduced the same can also be used.
  • the compounds of this type may function even in the absence of any other reducing agent, they are advantageously free from the problem of stain of images by the oxidized and decomposed product of a reducing agent.
  • Specific examples of the compounds are described in U.S. Patents 3,928,312, 4,053,312, 4,055,423 and 4,336,322, JP-A-59-­65839, JP-A-59-69839, JP-A-53-3819 and JP-A-51-104343, RD Item No. 17643, U.S.
  • Patents 3,725,062, 3,728,113 and 3,443,939, JP-A-58-116537 and JP-A-57-179840 and U.S. Patent 4,500,626 As preferred examples of such DRR compounds, the compounds described in the above-­mentioned U.S. Patent 4,500,626, columns 22 to 44 are referred to. Above all, Compounds (1) to (3), (10) to (13), (16) to (19), (28) to (30), (33) to (35), (38) to (40) and (42) to (64) described in U.S. Patent 4,500,626 are preferred. In addition, the compounds described in U.S. Patent 4,639,408, columns 37 to 39 are also useful.
  • dye-silver compounds comprising an organic silver salt and a dye as bonded to each other (RD of May 1978, pages 54 to 58), azo dyes to be employable in heat-­developing silver dye bleaching method (U.S. Patent 4,235,957, RD of April 1976, pages 30 to 32) and leuco dyes (U.S. Patents 3,985,565 and 4,022,617) can also be employed in the present invention.
  • the diffusive reducing agent which is employable in the present invention is a compound having an ability of developing silver halides and having a possibility of moving in the coated layers.
  • diffusive reducing agent anyone of compounds capable of developing a silver halide to give an oxidation product which reacts with the dye donor compound by coupling reaction (color developing agents) or compounds capable of developing a silver halide to give an oxidation product which oxidizes the dye donor compound directly or via a non-­diffusive reducing agent called an electron donor by cross-oxidation (electron-transmitting agents) can be employed in the present invention.
  • reducing agent there are dihydroxybenzenes, catechols, pyrogallols, 3-pyrazolidones, p-phenylenediamines, p-­aminophenols, sulfonamidophenols and hydrazones.
  • Patents 4,500,626 (columns 49 to 50), 4,483,914 (columns 30 to 31), 4,330,617 and 4,590,152, JP-A-60-140335 (pages 17 to 18), JP-A-57-40245, JP-A-56-138736, JP-A-59-178458, JP-A-59-53831, JP-A-59-182449, JP-A-59-182450, JP-A-60-­119555, JP-A-60-128436 to JP-A-60-128439, JP-A-60-­198540, JP-A-60-181742, JP-A-61-259253, JP-A-62-244044, JP-A-62-131253 to JP-A-62-131256 and European Patent 220,746A2 (pages 78 to 96).
  • Especially preferred diffusive reducing agents for use in the present inventions are compounds represented by the following formula (X-I) or (X-II): wherein R′ represents an aryl group; R31, R32, R33, R34, R35 and R36 each represents a hydrogen atom, a halogen atom, an acylamino group, an alkoxy group, an alkylthio group, an alkyl group or an aryl group and these may be same or different.
  • the aryl group for R′ in the formulae (X-I) and (X-II) includes, for example, a phenyl group, a naphthyl group, a tolyl group and a xylyl group. These groups may optionally be substituted.
  • R′ may be an aryl group optionally substituted by substituents selected from a halogen atom (e.g., chlorine, bromine), an amino group, an alkoxy group, an aryloxy group, a hydroxyl group, an aryl group, a carbonamido group, a sulfonamido group, an alkanoyloxy group, a benzoyloxy group, an ureido group, a carbamate group, a carbamoyloxy group, a carbonate group, a carboxyl group, a sulfo group and an alkyl group (e.g., methyl ethyl, propyl).
  • a halogen atom e.g., chlorine, bromine
  • the alkyl group for R31, R32, R33, R34, R35 and R36 in the formulae (X-I) and (X-II) is an alkyl group having from 1 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl), and the alkyl group may optionally be substituted by a hydroxyl group, an amino group, a sulfo group and/or a carboxyl group.
  • the aryl group there are phenyl group, naphthyl group, xylyl group and tolyl group.
  • the aryl group may be substituted by substituent(s) selected from a halogen atom (e.g., chlorine, bromine), an alkyl group (e.g., methyl ethyl, propyl), a hydroxyl group, an alkoxy group (e.g., methoxy, ethoxy), a sulfo group and a carboxyl group.
  • a halogen atom e.g., chlorine, bromine
  • an alkyl group e.g., methyl ethyl, propyl
  • a hydroxyl group e.g., an alkoxy group (e.g., methoxy, ethoxy)
  • a sulfo group e.g., methoxy, ethoxy
  • R31, R32, R33, and R34 each are preferably a hydrogen atom, a substituted alkyl group having from 1 to 10 carbon atoms or a substituted or unsubstituted aryl group, more preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a phenyl group or hydroxyl group or a phenyl group substituted by hydrophilic group(s) of an alkoxy group, a sulfo group and a carboxyl group.
  • Precursors of diffusive reducing agents indicate such compounds that do not have a developing action in storage of the photographic material before use but may release a reducing agent only by the action of a pertinent activating agent (for example, bases, nucleo­philic agents) or by the action of heat.
  • a pertinent activating agent for example, bases, nucleo­philic agents
  • the precursor does not have a function as a reducing agent before development but may function as a reducing agent under an alkaline condition or under heat because of the cleavage and removal of the blocking group.
  • reducing agent precursors for use in the present invention there are mentioned, for example, 2- and 3-acyl derivatives or 2-aminoalkyl or hydroxyalkyl derivatives of 1-phenyl-3-pyrazolidinone, metal salts (e.g., cadmium, calcium or barium salt) of hydroquinone or catechol, halogenated acyl derivatives of hydroquinone, oxazine or bisoxazine derivatives of hydroquinone, lactone-type ETA (electron transferring atent) precursors, quaternary ammonium group containing hydroquinone derivatives, cyclohexakis-2-ene-1,4-dione type compounds; as well as compounds of releasing a reducing agent by electron transfer reaction, compounds of releasing a reducing agent by intramolecular nucleophilic substitution reaction, reducing precursors blocked with phthalide group, and reducing agent precursors blocked with indomethyl group.
  • metal salts e.g., cadmium,
  • the reducing agent precursors for use in the present invention are known compounds; and developing agent precursors described in, for example, U.S. Patents 767,704, 3,241,967, 3,246,988, 3,295,978, 3,462,266, 3,586,506, 3,615,439, 3,650,749, 4,209,580, 4,330,617 and 4,310,612, British Patents 1,023,701, 1,231,830, 1,258,924 and 1,346,920, JP-A-57-40245, JP-A-58-1139, JP-A-58-1140, JP-A-59-178458, JP-A-59-183449 and JP-A-­59-182450 can be employed.
  • precursors of 1-phenyl-3-­pyrazolidinones described in JP-A-59-178458, JP-A-59-­182449 and JP-A-59-182450 are preferred.
  • the amount of the diffusive reducing agent and/or the diffusive reducing agent precursor for use in the present invention may vary in a broad range, but preferably, it is from 0.001 mol to 5 mols, more preferably from 0.01 mol to 1.5 mols, per mol of silver halide.
  • a non-diffusive reducing agent which is called an electron donor can be employed together with the diffusive reducing agent in the present invention. Combination use of such non-­diffusive reducing agent is preferred when the compounds belonging to the above mentioned group (3) are employed as the color donor compounds.
  • the electron donor is preferably incorporated into the photographic material in the vicinity of the dye donor compound and therefore it is added to the layer containing the dye donor compound. More preferably, it is added to the same phase as that containing the dye donor compound.
  • electron donors for use in the present invention there are mentioned non-diffusive group-containing dihydroxy­ benzenes, catechols, pyrogallols, sulfonamidophenols and sulfonamidonaphthols, as well as the reducing agents and/or precursors thereof described in European Patent Application 220746A (pages 84 to 95), JP-A-63-262647 and JP-A-1-142631.
  • compounds of the same kind as the compounds of the formula (I) can also be used as the electron donor.
  • hydrophobic additives such as dye donor compounds and electron donors can be introduced into the layers of the photographic materials by the same dispersion method as that for the compounds of the formula (I) mentioned above.
  • the photographic material of the present invention can contain a compound having a function of activating the developability thereof and of stabilizing the image formed.
  • a compound having a function of activating the developability thereof and of stabilizing the image formed are described in U.S. Patent 4,500,626, columns 51 to 52.
  • a dye-fixing material is employed together with the light-sensitive photographic material.
  • the system may be classified into two major categories, an embodiment in which the light-sensitive element and the dye-fixing element are respectively disposed on two independent supports and another embodiment in which the two elements are provided as coating layers on one and same support.
  • the relation between the light-sensitive photographic material and the dye-fixing material the relation thereof to the support and the relation thereof to the white reflective layer, those described in U.S. Patent 4,500,626, column 57 are applicable to the present invention.
  • the dye-fixing material which is preferably used in the present invention has at least one layer containing a mordant agent and a binder.
  • a mordant agent anyone known in the photographic field can be employed, and specific examples thereof include the mordant compounds described in U.S. Patent 4,500,626, columns 58 to 59 and JP A-61-88256, pages 32 to 41; and those described in JP-A-62-244043 and JP-A-62-244036.
  • dye-receiving high polymer compounds for example those described in U.S. Patent 4,463,079 can also be employed.
  • the dye-fixing material may optionally have, if desired, auxiliary layers such as protective layers, peeling layers and curling preventing layers.
  • auxiliary layers such as protective layers, peeling layers and curling preventing layers.
  • provision of the protective layer on the material is helpful.
  • the layers constituting the light-sensitive photographic material and dye-fixing material can contain a high boiling point organic solvent as the plasticizer, sliding agent or agent of improving peeling of the photographic material and the dye-fixing material from each other.
  • a high boiling point organic solvent as the plasticizer, sliding agent or agent of improving peeling of the photographic material and the dye-fixing material from each other.
  • silicone oils which may be all silicone oils including dimethylsilicone oil and modified silicone oils formed by introducing various organic groups into dimethylsiloxane
  • silicone oils there are mentioned various modified silicone oils described in Modified Silicone Oils (technical data published by Shin-Etsu Silicone Co.), pages 6 to 18B.
  • carboxy-modified silicone oil (trade name: X-22-3701 made by Shin-Etsu Silicone Co.) is effective.
  • silicone oils described in JP-A-62-­215958 and JP-A-63-46449 are also useful.
  • the light-sensitive photographic material and the dye-fixing material can contain an anti-fading agent.
  • anti-fading agent includes an antioxidant, an ultraviolet absorbent as well as various kinds of metal complexes.
  • antioxidant there are chroman compounds, coumaran compounds, phenol compounds (e.g., hindered phenols), hydroquinone derivatives, hindered amine derivatives and spyroindane compounds.
  • chroman compounds e.g., coumaran compounds
  • phenol compounds e.g., hindered phenols
  • hydroquinone derivatives e.g., hindered amine derivatives
  • spyroindane compounds e.g., chroman compounds, coumaran compounds, phenol compounds (e.g., hindered phenols), hydroquinone derivatives, hindered amine derivatives and spyroindane compounds.
  • the compounds described in JP-A-159644 are also effective.
  • the ultraviolet absorbent there are benzotriazole compounds (U.S. Patent 3,533,796), 4-­thiazolidone compounds (U.S. Patent 3,352,681), benzo­phenone compounds (JP-A-46-2784) and other compounds described in JP-A-54-48535, JP-A-62-136641 and JP-A-61-­38256. Further, the ultraviolet-absorbing polymers described in JP-A-62-260152 are also effective.
  • metal complexes there are mentioned the compounds described in U.S. Patents 2,241,155, 4,245,013 (columns 3 to 36) and 4,254,195 (columns 3 to 8), JP-A-62-174741, JP-A-61-88256 (pages 27 to 29), JP-A-1-75568 and JP-A-63-199248.
  • the anti-fading agent for preventing the dye as transferred to the dye-fixing material from fading may previously be incorporated into the dye-fixing material or, alternatively, it may be supplied to the dye-fixing material from an external source of the agent-containing light-sensitive photographic material.
  • antioxidant, ultraviolet absorbent and metal complex can be employed in the present invention in the form of a combination thereof.
  • the light-sensitive photographic material and the dye-fixing material can contain a brightening agent.
  • a brightening agent in the dye-fixing material or to supply the same to the said material from an external source of the agent-containing light-sensitive photographic material.
  • the agent the compounds described in K. Venkataraman, The Chemistry of Synthetic Dyes , Vol. V, Chap. 8, and JP-A-61-143752 are referred to.
  • a fluorescent whitening agent can be employed in combination with the anti-fading agent.
  • the layers constituting the light-sensitive photographic material and dye-fixing material can contain a hardening agent.
  • a hardening agent As examples thereof, the hardening agents described in U.S. Patent 4,678,739 (column 41) and JP-A-59-116655, JP-A-62-245261 and JP-A-­61-18942 are mentioned.
  • aldehyde hardening agents e.g., form­aldehyde
  • aziridine hardening agents epoxy hardening agents
  • vinylsulfone hardening agents e.g., N,N′-ethylene-bis­(vinylsulfonylacetamido)ethane
  • N-methylol hardening agents e.g., dimethylolurea
  • high polymer hardening agents e.g., compounds described in JP-A-62-234157.
  • the layers constituting the light-sensitive photographic material and dye-fixing material can contain various surfactants for various purposes of coating aid, improvement of peeling property, improve­ment of slide property, prevention of static charges and enhancement of developability. Specific examples of such surfactants are described in JP-A-62-173463 and JP-­A-62-183457.
  • the layers constituting the light-sensitive photographic material and dye-fixing material can contain organic fluoro compounds for the purposes of improvement of slide property, prevention of static charges and improvement of peeling property.
  • organic fluoro compounds there are mentioned fluorine surfactants described in JP-B-57-9053 (columns 8 to 17) and JP-A-61-20944 and JP-­A-62-135826, as well as hydrophobic fluorine compounds such as fluorine oils and the like oily fluorine compounds and ethylene tetrafluoride resins and the like solid fluorine compound resins.
  • the light-sensitive photographic material and dye-fixing material can contain a mat agent.
  • a mat agent there are mentioned silicone dioxide and the compounds described in JP-A-61-88256 (page 29) such as olefins or polymethacrylates, as well as the compounds described JP-A-63-274944 and JP-A-63-274952 such as benzoguanamine resin beads, polycarbonate resin beads and AS (acrylonitrile-styrene) resin beads.
  • the layers constituting the light-­sensitive photographic material and dye-fixing material may further contain a thermal solvent, a defoaming agent, a microbicidal and fungicidal agent, a colloidal silica and other additives. Examples of such additives are described in JP-A-61-88256 (pages 26 to 32).
  • the light-sensitive photographic material and/or the dye-­fixing material can contain an image formation accelerator.
  • the image formation accelerators include those which promote the redox reaction between the silver salt oxidizing agent and the reducing agent, those which promote the reactions of forming a dye from a dye donor substance or decomposing a dye or releasing a diffusive dye, and those which promote the migration of the dye from the photosensitive layer to the dye-­fixing layer.
  • Classified by physicochemical function the image formation accelerators can be classified into bases or base precursors, nucleophilic compounds, high boiling point organic solvents (oils), hot-melting solvents, surfactants and compounds which interact with silver or silver ions, for instance.
  • each of these substances generally has plural functions and provides several of the above-mentioned effects. A detailed discussion on these substances can be found in U.S. Patent 4,678,739, columns 38 to 40.
  • the base precursor there are mentioned salts of an organic acid which may be decarboxylated under heat and a base, as well as compounds capable of releasing an amine by intramolecular nucleophilic substitution reaction, Rossen rearrangement or Backmann rearrangement. Specific examples thereof are described in U.S. Patent 4,511,493 and JP-A-62-65038.
  • the base and/or base precursor in the dye-fixing material for the purpose of improving the storage stability of the light-sensitive photographic material.
  • a hardly soluble metal compound and a compound capable of complexing with the metal ion which constitutes the said hardly soluble metal compound (hereinafter referred to as "complex-­forming compound") described in European Patent Application 210,660A as well as the compounds of giving a base by electrolysis described in JP-A-61-232451 can also be used as the base precursor.
  • Use of the former is especially effective.
  • the hardly soluble metal compound and the complex-forming compound are advantageously separately added to different light-­sensitive photographic material and dye-fixing material.
  • the light-sensitive photographic material and/or the dye-fixing material of the present invention can contain various development stopping agents for the purpose of always obtaining constant images despite fluctuation of the development temperature and processing time in development.
  • development stopping agent means a compound which, after proper development, quickly neutralizes the base or reacts with the base to lower the base concentration in the layer and thereby terminates the development or a compound which interacts with silver and silver salt to arrest development.
  • acid precursors which releases an acid under heat
  • electrophilic compounds which react with the existing base by substitution reaction under heat
  • nitrogen-containing heterocyclic compounds mercapto compounds and precursors thereof. More precisely, the compounds are described in JP-A-62-253159 (pages 31 to 32).
  • the support which is employable in the light-­sensitive photographic material and dye-fixing material may be any support that withstands the processing temperature.
  • paper and synthetic high polymer films are used as the support.
  • the support includes films of polyethylene terephtha­late, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, celluloses (e.g., triacetyl cellulose) and those films containing a pigment such as titanium oxide; synthetic paper made of polypropylene by filming method; mixed paper made of a synthetic resin pulp (e.g., polyethylene) and a natural pulp; as well as Yankee paper, baryta paper, coated paper (especially cast-coated paper), metals, cloth and glass.
  • These supports may be used directly as they are or may be used in the form as coated with a synthetic high polymer substance (e.g., polyethylene) on one surface or both surfaces thereof.
  • a synthetic high polymer substance e.g., polyethylene
  • the surface of the support may be coated with a hydrophilic binder and a semiconductive metal oxide (e.g., alumina sol or tin oxide) or an antistatic agent such as carbon black.
  • a semiconductive metal oxide e.g., alumina sol or tin oxide
  • an antistatic agent such as carbon black.
  • various methods can be employed, which include, for example, a method of directly photographic scene or portrait with a camera; a method of exposing through a reversal film or negative film by the use of a printer or an enlarger; a method of scanning and exposing an original through a slit by the use of an exposing device of a duplicator; a method of exposing an image information via the corresponding electric signal by emitting the same with a light emitting diode or various lasers; and a method of outputting an image information with an image display device such as CRT (cathode-ray tube), liquid crystal display, electroluminescence display or plasma display and then exposing the same directly or via some optical system.
  • CTR cathode-ray tube
  • the light source to be used for recording an image on the photographic material those described in U.S. Patent 4,500,626 (column 56), such as natural light, tungusten lamp, light-emitting diode, laser rays and CRT rays can be employed, as mentioned above.
  • a wavelength converting element comprising a combination of a non-linear optical material and a coherent light source such as laser rays can also be used for image exposure.
  • non-linear optical material as used herein means a material capable of expressing non-linear property between the polarization to be caused by some strong photoelectric field such as laser rays and the electric field.
  • inorganic compounds such as lithium niobate, potassium dihydrogenphosphate (KDP), lithium iodate and BaB2O4, as well as urea derivatives, nitro­ aniline derivatives, nitropyridine-N-oxide derivatives (e.g., 3-methyl-4-nitropyridine-N-oxide (POM)) and the compounds described in JP-A-61-54362 and JP-A-62-210432 are preferably employed in the present invention.
  • KDP potassium dihydrogenphosphate
  • Li iodate lithium iodate
  • BaB2O4 lithium niobate
  • urea derivatives such as lithium niobate, potassium dihydrogenphosphate (KDP), lithium iodate and BaB2O4
  • urea derivatives such as lithium niobate, potassium dihydrogenphosphate (KDP), lithium iodate and BaB2O4, as well as urea derivatives, nitro­ aniline derivatives, nitropyridine-N-
  • the image information to be applicable to the photographic material of the present invention anyone of the image signal to be obtained from video camera or electronic still camera; the television signal as standardized by Japan Television Signal Standard (NTSC); the image signal obtained by dividing the original into plural elements with scanner; and the image signal formed by the use of computer such as CG (computer graphics) or CAD (computer assisted drawing), can be employed.
  • NTSC Japan Television Signal Standard
  • CAD computer assisted drawing
  • the light-sensitive photographic material and/or the dye-fixing material may be in such form that has an electroconductive heating element layer as the heating means for heat development and diffusion and transfer of the formed dyes.
  • the heating element may be either transparent or opaque, and the elements described in JP-A-61-145544 can be employed.
  • the electroconductive layer acts also as an antistatic layer.
  • the heating temperature in the heat-development step may be from about 50°C to about 250°C. Especially preferably, the temperature is from about 80°C to about 180°C.
  • the step of diffusing and transferring the dye formed by the development may be effected simultaneously with the heat-development step or after the same. In the latter case, the heating temperature in the transfer step may be from the temperature in the previous heat-­development step to room temperature. Preferably, it is from 50°C to a temperature lower than the temperature in the heat-development step by about 10°C.
  • Migration of the dye formed may be effected only by heat, but a solvent may be used for the purpose of accelerating the migration of the dye.
  • the method where development and transfer are carried out in the presence of a small amount of a solvent, especially water, either at the same time or in a continuous sequence can be advantageously utilized.
  • the heating temperature is preferably higher than 50°C and lower than the boiling point of the solvent used.
  • the temperature is desirably from 50°C to 100°C.
  • the solvents to be used for acceleration of development and/or migration of the diffusive dye formed to the dye-fixing material there are mentioned water and an aqueous basic solution containing an inorganic alkali metal salt or an organic base.
  • the bases those mentioned hereinbefore for the image formation accelerators can be employed.
  • a low boiling point solvent or a mixed solvent comprising a low boiling point and water or an aqueous basic solution can also be used.
  • surfactants, antifoggant as well as hardly soluble metals and complex-forming compounds can be incorporated into the solvents.
  • the solvent can be used by applying the same to either the dye-fixing material or the light-sensitive photographic material or to both of them.
  • the amount thereof to be used may be a small amount of less than the weight of the solvent corresponding to the maximum swollen volume of the total coated layers (especially less than the amount obtained by subtracting the weight of the total coated layers from the weight of the solvent corresponding to the maximum swollen volume of the total coated layers).
  • the solvent can be incorporated into either the light-sensitive photo­graphic material or the dye-fixing material or into both of them in the form of solvent-containing microcapsules.
  • a system of incorporating a hydrophilic thermal solvent which is solid at room temperature but may melt at a high temperature into the light-sensitive photographic material or into the dye-fixing material may also be employed in the present invention.
  • the hydrophilic thermal solvent may be incorporated in either the light-sensitive photographic material or the dye-fixing material or in both of them.
  • the layer to which the solving is added may be any of the emulsion layer, interlayer, protective layer and dye-fixing layer, but the solvent is preferably added to the dye-fixing layer and/or the adjacent layer(s).
  • thermal solvent to be employed in the system there are mentioned ureas, pyridine, amides, sulfonamides, imides, oximes, alcohols and other heterocyclic compounds.
  • a high boiling point organic solvent may be incorporated into the light-sensitive photographic material and/or the dye-fixing material.
  • the material may be contacted with a heated block or plate, or with a hot plate, hot presser, hot roller, halogen lamp heater or infrared or far-infrared lamp heater or is passed through a high temperature atmosphere.
  • JP-A-59-75247, JP-A-59-177547, JP-A-59-­181353 and JP-A-60-18951 and JP-A-U-62-25944 are preferably employed.
  • JP-A-U as used herein means an "unexamined published Japanese utility model application”.
  • Emulsion (I) for the first layer was prepared as mentioned below.
  • Solution (I), Solution (II) and Solution (III) were simultaneously added to a well stirred aqueous gelatin solution (prepared by adding 20 g of gelatin, 1 g of potassium bromide and 0.5 g of OH(CH2)2S(CH2)2OH to 800 ml of water and heated at 50°C), all at the same flow rate over a period of 30 minutes. Accordingly, a dye-adsorbed monodispersed silver bromide emulsion having mean grain size of 0.42 ⁇ m was prepared.
  • Emulsion (II) for the third layer was prepared as mentioned below.
  • Solution (I) and Solution (II) were simultaneously added to a well stirred aqueous gelatin solution (prepared by adding 20 g of gelatin, 0.30 g of potassium bromide, 6 g of sodium chloride and 0.015 g of the following Compound (A) to 730 ml of water and heated at 60.0°C), all at the same flow rate over a period of 60 minutes.
  • aqueous gelatin solution prepared by adding 20 g of gelatin, 0.30 g of potassium bromide, 6 g of sodium chloride and 0.015 g of the following Compound (A) to 730 ml of water and heated at 60.0°C), all at the same flow rate over a period of 60 minutes.
  • Solution (III) sensensitizing dye-­containing methanol solution
  • Emulsion (III) for the fifth layer was prepared as mentioned below.
  • Solution (I) and Solution (II) were simultaneously added to a well stirred aqueous gelatin solution (prepared by adding 30 g of gelatin, 3 g of potassium bromide, and 0.5 g of HO(CH2)2S(CH2)2S­(CH2)2OH to 600 ml of water and heated at 65°C) over a period of 20 minutes. Afterwards, the following Solution (III) and Solution (IV) were simultaneously added thereto over a period of 30 minutes. After rinsed with water and desalted, 20 g of lime-processed ossein gelatin was added and the resulting emulsion was adjusted to pH of 6.2 and pAg of 8.5.
  • the dye donor substance-containing gelatin dispersion was prepared as follows:
  • Magenta dye donor substance dispersion and cyan dye donor substance dispersion were also prepared in the same manner as the yellow dye donor substance disper­sion, but using Magenta Dye Donor Substance (2)* and Cyan Dye Donor Substance (3)*, respectively.
  • a multilayer color photographic material (Sample No. 101) having the layers mentioned below was prepared.
  • Sixth Layer Protective Layer Gelatin 0.90 g/m2 Mat agent (silica) 0.03 g/m2 Water-soluble polymer (1)* 0.02 g/m2 Surfactant (1)* 0.06 g/m2 Surfactant (2)* 0.13 g/m2 Hardening agent (1)* 8 ⁇ 10 ⁇ 3 g/m2 Zn(OH)2 0.45 g/m2
  • Fifth Layer Blue Light-sensitive Layer Emulsion (III) 0.33 g/m2 as Ag Gelatin 0.56 g/m2 Antifoggant (2)* 5.0 ⁇ 10 ⁇ 4 g/m2 Yellow dye donor substance (1)* 0.40 g/m2 High boiling point organic solvent (1)* 0.20 g/m2 Electron donor (1)* 0.27 g/m2 Surfactant (3)* 0.05 g/m2 Hardening agent (1)* 8 ⁇ 10 ⁇ 3 g/m2 Water
  • the reducing agent (1)* was dispersed in the high boiling point organic solvent (1)* as mentioned below and added to the layers.
  • Samples Nos. 102 to 105 were prepared in the same manner as Sample No. 101, except that the reducing agent (1)* in the second layer and the fourth layer was replaced by the same molar amount of the compound of the present invention as indicated in Table 1 below.
  • Sample No. 106 was prepared also in the same manner as Sample No. 101, except that the amount of the reducing agent (1)* in the second layer and the fourth layer was increased twice.
  • Third Layer Gelatin 0.05 g/m2 Silicone oil (*1) 0.04 g/m2 Surfactant (*2) 0.001 g/m2 Surfactant (*3) 0.02 g/m2 Surfactant (*4) 0.10 g/m2 Guanidine picolinate 0.45 g/m2 Polymer (*5) 0.24 g/m2
  • Second Layer Mordant agent (*6) 2.35 g/m2 Polymer (*7) 0.60 g/m2 Gelatin 1.40 g/m2 Polymer (*5) 0.21 g/m2 High boiling point solvent (*8) 1.40 g/m2 Guanidine picolinate 1.80 g/m2 Surfactant (*2) 0.02 g/m2 First Layer : Gelatin 0.45 g/m2 Surfactant (*4) 0.01 g/m2 Polymer (*5) 0.04 g/m2 Hardening agent (*9) 0.30 g/m2
  • Polyethylene-laminated paper (thickness: 170 ⁇ m) support
  • First Baking Layer Gelatin 3.25 g/m2 Hardening agent (*9) 0.23 g/m2
  • Second Backing Layer Gelatin 0.44 g/m2 Silicone oil (*1) 0.08 g/m2 Surfactant (*2) 0.002 g/m2 Mat agent (*10) 0.09 g/m2
  • the combined sample was heated with a heat roller whose temperature was so adjusted that the temperature of the water-absorbed surface could be 80°C, for 15 seconds.
  • the image-receiving material was peeled off from the light-sensitive material, and a spectrogram of blue, green and red corresponding to the wavelength was formed on the dye-fixing material.
  • the organic silver salt emulsion was prepared as mentioned below.
  • Sixth Layer Protective Layer Gelatin 0.91 g/m2 Mat agent (silica) 0.03 g/m2 Surfactant (1)* 0.06 g/m2 Surfactant (2)* 0.13 g/m2 Hardening agent (1)* 0.01 g/m2 Base precursor (1)* 0.30 g/m2 Water-soluble polymer (1)* 0.03 g/m2
  • Fifth Layer Blue-sensitive Layer Emulsion (III) 0.30 g/m2 as Ag Organic silver salt emulsion 0.25 g/m2 as Ag Gelatin 1.00 g/m2 Antifoggant (3)* 1.6 ⁇ 10 ⁇ 2 g/m2 Yellow dye donor compound (4)* 0.30 g/m2 High boiling point organic solvent (1)* 0.75 g/m2 Surfactant (3)* 0.05 g/m2 Developing agent precursor (1)* 0.10 g/m2 Thermal solvent (1)* 0.20 g/m2 Hardening agent (1)* 0.01 g/m2 Base precursor (1)* 0.27 g/m2 Water-soluble polymer (1)* 0.03
  • Samples Nos. 202 to 205 were prepared in the same manner as Sample No. 201, except that the reducing agent (2)* in the second layer and fourth layer was replaced by the same molar amount of the same compound of the present invention as that in Example 1, respectively.
  • a dye-fixing material (Sample R-2) was prepared as follows:
  • Example 2 The previously prepared photographic material samples were exposed in the same manner as Example 1 and then uniformly heated on a heat block heated at 150°C for 30 seconds.
  • the thus combined sample was passed through a laminater heated at 80°C at a linear velocity of 12 mm/sec and then the both materials were peeled off from each other.
  • the dye-fixing material sample had a negative image thereon.
  • the color density of cyan and magenta in the blue light portion, that of cyan and yellow in the green light portion and that of magenta and yellow in the red light portion were measured with an X-Rite 310 TR densitometer and the results were shown in Table 2 below.
  • the yellow density in the blue light portion was from 1.9 to 2.0
  • the magenta density of the green light portion was from 2.0 to 2.1
  • the cyan density in the red light portion was from 2.0 to 2.1.
  • the organic silver salt emulsion used was same as that used in Example 2.
  • the antifoggant precursor (1)* having the structure mentioned below was added to the dye donor substance in an amount of 0.2 mol times that of the substance and was formed into an oil dispersion together with the dye donor substance and electron donor, like the method of Example 1.
  • Sixth Layer Protective Layer Gelatin 0.91 g/m2 Mat agent (silica) 0.03 g/m2 Surfactant (1)* 0.06 g/m2 Surfactant (2)* 0.13 g/m2 Water-soluble polymer (1)* 0.03 g/m2 Hardening agent (1)* 0.01 g/m2 Base precursor (1)* 0.30 g/m2 Fifth Layer : Blue-sensitive Layer Emulsion (III) 0.30 g/m2 as Ag Organic silver salt emulsion 0.25 g/m2 as Ag Gelatin 1.00 g/m2 Antifoggant precursor (1)* 0.07 g/m2 Yellow dye donor substance (4)* 0.50 g/m2 High boiling point organic solvent (1)* 0.75 g/m2 Electron donor (1)* 0.47 g/m2 Surfactant (3)* 0.05 g/m2 Electron-transmitting agent (2)* 0.04 g/m2 Thermal solvent (1)* 0.20 g/m2 Hardening agent (1)* 0.01 g/m2 Base precursor (1)* 0.27 g
  • Example 2 The samples prepared above were exposed in the same manner as in Example 1 and then uniformly heated on a heat block heated at 140°C for 30 seconds.

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
EP19890116013 1988-08-31 1989-08-30 Wärmeentwickelbares photographisches Farbmaterial und Bildherstellungsverfahren damit Expired - Lifetime EP0357040B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP21727188A JPH0264633A (ja) 1988-08-31 1988-08-31 熱現像カラー感光材料およびそれを用いた画像形成方法
JP217271/88 1988-08-31

Publications (2)

Publication Number Publication Date
EP0357040A1 true EP0357040A1 (de) 1990-03-07
EP0357040B1 EP0357040B1 (de) 1995-05-10

Family

ID=16701526

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19890116013 Expired - Lifetime EP0357040B1 (de) 1988-08-31 1989-08-30 Wärmeentwickelbares photographisches Farbmaterial und Bildherstellungsverfahren damit

Country Status (3)

Country Link
EP (1) EP0357040B1 (de)
JP (1) JPH0264633A (de)
DE (1) DE68922551T2 (de)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2879623B2 (ja) * 1991-07-26 1999-04-05 富士写真フイルム株式会社 カラー感光材料

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0123904A1 (de) * 1983-03-29 1984-11-07 Fuji Photo Film Co., Ltd. Wärmeentwickelbares photographisches Material
EP0218385A2 (de) * 1985-09-17 1987-04-15 Konica Corporation Wärmeentwickelbares lichtempfindliches Material

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5937497A (ja) * 1982-08-25 1984-02-29 富士電機株式会社 原子炉の燃料移送設備
JPS59202465A (ja) * 1983-05-04 1984-11-16 Fuji Photo Film Co Ltd カラ−写真感光材料
JPS60119555A (ja) * 1983-12-02 1985-06-27 Konishiroku Photo Ind Co Ltd 熱現像カラ−感光材料
JPS60133449A (ja) * 1983-12-22 1985-07-16 Konishiroku Photo Ind Co Ltd 熱現像カラ−感光材料
JPH07107601B2 (ja) * 1985-07-26 1995-11-15 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
JPH061360B2 (ja) * 1985-12-25 1994-01-05 富士写真フイルム株式会社 ハロゲン化銀カラ−写真感光材料
JPS62203158A (ja) * 1986-03-03 1987-09-07 Fuji Photo Film Co Ltd 熱現像カラ−感光材料
JPH0690470B2 (ja) * 1986-12-26 1994-11-14 富士写真フイルム株式会社 ハロゲン化銀カラ−写真感光材料

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0123904A1 (de) * 1983-03-29 1984-11-07 Fuji Photo Film Co., Ltd. Wärmeentwickelbares photographisches Material
EP0218385A2 (de) * 1985-09-17 1987-04-15 Konica Corporation Wärmeentwickelbares lichtempfindliches Material

Also Published As

Publication number Publication date
DE68922551T2 (de) 1995-08-17
EP0357040B1 (de) 1995-05-10
DE68922551D1 (de) 1995-06-14
JPH0264633A (ja) 1990-03-05

Similar Documents

Publication Publication Date Title
EP0459416B1 (de) Farbstoff-Fixierelement
JP2893152B2 (ja) 熱現像感光材料
US5725990A (en) Image formation method
EP0411466B1 (de) Wärmeentwickelbares farbphotographisches lichtempfindliches Material
US5316886A (en) Heat developable photosensitive materials
EP0386669B1 (de) Lichtempfindliches Farbmaterial
EP0334362B1 (de) Wärmeentwickelbares, lichtempfindliches Farbmaterial
EP0386761B1 (de) Wärmeentwickelbares lichtempfindliches Farbmaterial
US5401622A (en) Thermally developable color photosensitive materials with U.V. absorbers
US5051348A (en) Heat-developable color light-sensitive material
EP0357040B1 (de) Wärmeentwickelbares photographisches Farbmaterial und Bildherstellungsverfahren damit
US5478693A (en) Diffusion transfer heat-developable color photographic light-sensitive material and process for forming color image
US5558973A (en) Heat-developable color light-sensitive material and method for producing the same
US5156939A (en) Heat-developable light-sensitive material
JP2655192B2 (ja) 熱現像感光材料
US5503969A (en) Heat-developable color light-sensitive material
EP0715209B1 (de) Wärmeentwickelbares lichtempfindliches Farbmaterial
JPS59182447A (ja) 乾式画像形成のための色素固定材料
JP2767348B2 (ja) 色素固定要素
JP2655187B2 (ja) 熱現像カラー感光材料
JP2931720B2 (ja) ハロゲン化銀感光材料
JP2649853B2 (ja) 拡散転写写真材料
JP3242777B2 (ja) 色素固定要素
JP2579196B2 (ja) 熱現像カラー感光材料
JP2612206B2 (ja) カラー感光材料

Legal Events

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

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): DE GB

17P Request for examination filed

Effective date: 19900608

17Q First examination report despatched

Effective date: 19930302

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE GB

REF Corresponds to:

Ref document number: 68922551

Country of ref document: DE

Date of ref document: 19950614

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

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

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20080912

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20080903

Year of fee payment: 20

REG Reference to a national code

Ref country code: GB

Ref legal event code: PE20

Expiry date: 20090829

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20090829