EP0310125B1 - Matériau photgraphique couleur à l'halogénure d'argent - Google Patents

Matériau photgraphique couleur à l'halogénure d'argent Download PDF

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Publication number
EP0310125B1
EP0310125B1 EP88116247A EP88116247A EP0310125B1 EP 0310125 B1 EP0310125 B1 EP 0310125B1 EP 88116247 A EP88116247 A EP 88116247A EP 88116247 A EP88116247 A EP 88116247A EP 0310125 B1 EP0310125 B1 EP 0310125B1
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EP
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Prior art keywords
group
formula
silver halide
represented
photographic material
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EP88116247A
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German (de)
English (en)
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EP0310125A2 (fr
EP0310125A3 (en
Inventor
Kei Sakanoue
Hedetoshi Kobayashi
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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
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/305—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers
    • G03C7/30541—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers characterised by the released group
    • 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
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/3022—Materials with specific emulsion characteristics, e.g. thickness of the layers, silver content, shape of AgX grains

Definitions

  • the present invention relates to a silver halide color photographic material.
  • the fundamental steps of processing silver halide color photographic materials generally include a color development step and a desilvering step.
  • a color development step exposed silver halide is reduced with a color developing agent to form silver and the oxidized color developing agent reacts with a color former (coupler) to yield a dye image.
  • the silver thus formed is oxidized with a bleaching agent, further changed into a soluble silver complex by a fixing agent and then dissolved away.
  • bleach-fixing solutions which contain an aminopolycarboxylic acid ferric ion complex salt and a thiosulfate in a single solution, as described in DE-B- 866,605.
  • the bleaching ability of the solution is very weak since an aminopolycarboxylic acid ferric ion complex salt which per se is weak in oxidizing power (bleaching ability) and a thiosulfate which has a reducing power are coexistent in a single solution. Therefore, it is very difficult for the bleach-fixing solution to sufficiently achieve desilveration of color photographic materials, particularly for elements of high sensitivity and high silver content; consequently it cannot be employed for practical use.
  • bleach accelerating agents exhibit certain bleach accelerating effects, they are expensive compounds orthey are insufficiently stable in the bath having bleaching ability. Further, their bleach accelerating effect per se is still insufficient and thus they are not satisfactorily employed for practical use.
  • the mercapto compound may react with undeveloped silver halide or silver halide formed by a bleaching reaction present in an emulsion layer of a photographic material to form a sparingly soluble silver salt which is not solubilized by a fixing agent and, as a result, cause insufficient fixing.
  • silver ions are accumulated in the bleach-fixing bath.
  • Silver ions form a sparingly soluble silver salt with a mercapto compound. This reaction is particularly apt to occur in the case where iodide ions are present in the bleach-fixing bath employed.
  • a photographic light-sensitive material containing the above-described mercapto compound or a precursor thereof which is a bleach accelerating agent can be processed.
  • this method also has many problems in that the mercapto compound adversely affects photographic properties of the photographic light-sensitive material to which it is added and in that the mercapto compound reacts with silver halide at an undeveloped portion of the photographic material to form a sparingly soluble silver salt.
  • Aphotographic light-sensitive material containing a high silver iodide content emulsion is inferior in its desilvering property as compared to one with a low silver iodide content emulsion.
  • DE-A-3641861 relates to the desilverization of photographic materials containing silver iodobromide emulsions of high iodide content employed to obtain an improved graininess, said photographic materials comprising a support having thereon silver halide emulsion layers containing iodobromide grains of an average iodide content of 7 mol% or more and containing a naphthol type coupler and a DIR coupler.
  • a silver halide color photographic material comprising a support having thereon at least one silver halide emulsion layer, wherein the silver halide color photographic material contains at least one silver halide emulsion containing silver iodide grains whose average iodide content is at least 7 mol % and at least one compound capable of releasing a bleach accelerating agent upon reaction with an oxidation product of an aromatic primary amine type color developing agent, said compound having the following general formula (I): wherein A represents a group whose bond to (L1) a -(L 2 ) b -Z is capable of being cleaved upon reaction with an oxidation product of a developing agent; L 1 represents a timing group or a group whose bond to (L 2 ) b -Z is capable of being cleaved upon reaction with an oxidation product of a developing agent; L 2 represents a timing group or a group whose bond to Z is capable of being released upon
  • a deterioration in desilvering capability which occurs in photographic light-sensitive materials comprising a high silver iodide content emulsion and which could not be sufficiently prevented by using conventional bleach accelerating agents is effectively eliminated by means of the incorporation of the compound capable of releasing a bleach accelerating agent having the general formula (I).
  • silver halide emulsion having a high silver iodide content is determined by the solid solution limiting value to be 40 mol %.
  • a silver halide emulsion whose silver iodide content is preferably in a range from 8 mol % to 40 mol %, more preferably in a range from 10 mol % to 30 mol %, and further more preferably in a range from 12 mol % to 25 mol %, is employed together with the compound capable of releasing a bleach accelerating agent according to the present invention.
  • the silver iodide content is lower than the lower limit described above, the effect of the present invention generally decreases to some extent.
  • the grain size of the high iodide content silver halide emulsion according to the present invention may be appropriately selected, when the high iodide content silver halide emulsion which preferably has a grain size of not less than 0.8 f..lm, more preferably not less than 1.5 ⁇ m, is employed together with the compound capable of releasing a bleach accelerating agent according to the present invention, a color photographic light-sensitive material having high sensitivity and improved desilvering property is obtained.
  • the high iodide content emulsion which is used in the present invention can be prepared using various methods. Specifically, any of, e.g., an acid process, a neutral process and an ammonia process, can be employed. Further, soluble silver salts and soluble halogen salts can be reacted by techniques such as a single jet process, a double jet process, and a combination thereof.
  • a controlled double jet process in which the pAg in the liquid phase where silver halide is formed is maintained at a predetermined level can be employed.
  • a triple jet process in which soluble halogen salts having different compositions from each other are added individually (for example, a soluble silver salt, a soluble bromide and a soluble iodide) can also be employed.
  • a silver halide solvent for example, ammonia, thiocyanates, thioureas or amines as described in T.H. James ed., The Theory of the Photographic Process, Fourth Edition, page 9, Macmillan Publishing Co., Inc. (1977).
  • pH and pAg are controlled during the formation of silver halide grains so as to obtain preferred photographic properties.
  • the pH may be preferably varied in a range from 2 to 10, depending on the method for preparation of grains.
  • Silver halide grains in the high iodide content emulsion according to the present invention may have a regular crystal structure, for example, a hexahedral, octahedral, dodecahedral or tetradecahedral structure, or an irregular crystal structure, for example, a spherical or tabular structure.
  • the inner portion and the surface layer of the silver halide grains may be different in halogen composition or may be uniform.
  • Double structure grains in which the inner portion (core) is composed of silver iodochlorobromide or silver iodobromide containing a high concentration of silver iodide and the outer portion (shell) is composed of silver chloroiodobromide or silver iodobromide of a low silver iodide content are preferably employed in the emulsion according to the present invention.
  • the ratio of the silver amount in the core and the shell can be selected in a wide range, but is preferably in the range from 5/1 to 1/5 (core Ag amount/shell Ag amount).
  • the object of the present invention can be achieved by a silver halide emulsion in which the average value of the silver iodide content in the grains is not less than 7 mol %. More specifically, the silver iodide content in the core is preferably selected to be not less than 15 mol %, more preferably not less than 25 mol %, further more preferably from 35 mol % to the solid solution limiting value of silver iodobromide (refer to T.H. James ed., The Theory of the Photographic Process, Fourth Edition, page 4). On the other hand, the silver iodide content in the shell is preferably not more than 5 mol % and more preferably not more than 2 mol %.
  • the formation or physical ripening of the silver halide grains may be carried out in the presence of, e.g., cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts thereof, rhodium salts or complex salts thereof and iron salts or complex salts thereof.
  • cadmium salts zinc salts, lead salts, thallium salts, iridium salts or complex salts thereof, rhodium salts or complex salts thereof and iron salts or complex salts thereof.
  • the well known noodle washing process in which gelatin is gelated may be used.
  • a flocculation process utilizing inorganic salts having a polyvalent anion (for example, sodium sulfate), anionic surface active agents, anionic polymers (for example, polystyrene sulfonic acid), or gelatin derivatives for example, aliphatic acylated gelatin, aromatic acylated gelatin and aromatic carbamoylated gelatin, aromatic acylated gelatin and aromatic carbamoylated gelatin
  • a polyvalent anion for example, sodium sulfate
  • anionic surface active agents for example, polystyrene sulfonic acid
  • gelatin derivatives for example, aliphatic acylated gelatin, aromatic acylated gelatin and aromatic carbamoylated gelatin, aromatic acylated gelatin and aromatic carbamoylated gelatin
  • Silver halide emulsions are usually chemically sensitized.
  • chemical sensitization for example, the methods as described in H. Frieser ed., Die Unen der Photographischen Too mit Silberhalogeni- den, Akademische Verlagsgesellschaft, pages 675 to 734 (1968) can be used.
  • a sulfur sensitization using active gelatin or compounds for example, thiosulfates, thioureas, mercapto compounds and rhodanines
  • active gelatin or compounds for example, thiosulfates, thioureas, mercapto compounds and rhodanines
  • reducing substances for example, stannous salts, amines, hydrazine derivatives, formamidinesulfinic acid, and silane compounds
  • a noble metal sensitization using noble metal compounds for example, complex salts of Group VIII metals in the Periodic Table, such as, e.g., Pt, Ir and Pd, as well as gold complex salts
  • noble metal compounds for example, complex salts of Group VIII metals in the Periodic Table, such as, e.g., Pt, Ir and Pd, as well as gold complex salts
  • the photographic emulsion used in the present invention may include various compounds for the purpose of preventing fog formation or stabilizing photographic performance in the photographic light-sensitive material during the production, storage or photographic processing thereof.
  • compounds known as antifoggants or stabilizers can be incorporated, including for example azoles such as, e.g., benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitro- benzotriazoles and mercaptotetrazoles (particularly 1-phenyl-5-mercaptotetrazole); mercaptopyrimidines; mercaptotriazines; thioketo compounds such as, e.g., oxazolinethione; azaindenes such as
  • the photographic emulsion used in the present invention may also be spectrally sensitized with methine dyes or other dyes.
  • Suitable dyes which can be employed include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hem- ioxonol dyes. Of these dyes, cyanine dyes, merocyanine dyes and complex merocyanine dyes are particularly useful. Any conventionally utilized nucleus for cyanine dyes, such as basic heterocyclic nuclei, is applicable to these dyes.
  • nuclei having a keto-methylene structure 5-membered or 6-membered heterocyclic nuclei such as a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thioxazolidin-2,4-dione nucleus, a thiazolidin-2,4-dione nucleus, a rhodanine nucleus, and a thiobarbituric acid nucleus may also be used.
  • 5-membered or 6-membered heterocyclic nuclei such as a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thioxazolidin-2,4-dione nucleus, a thiazolidin-2,4-dione nucleus, a rhodanine nucleus, and a thiobarbituric acid nucleus may also be used.
  • Useful sensitizing dyes include those as described, for example, in DE-B-929,080, US-A-2,231,658, US-A-2,493,748, US-A-2,503,776, US-A-2,519,001, US-A-2,912,329, US-A-3,656,959, US-A-3,672,897, US-A-3,694,217, US-A-4,025,349 and US-A-4,046,572, GB-B-1,242,588, JP-B-44-14030 and JP-B-52-24844.
  • sensitizing dyes can be employed individually, and can also be employed in combination.
  • a combination of sensitizing dyes is often used, particularly for the purpose of supersensitization.
  • the sensitizing dyes may be present in the emulsion together with dyes which themselves do not give rise to any spectral sensitizing effects but exhibit a supersensitizing effect or materials which do not substantially absorb visible light but exhibit a supersensitizing effect.
  • aminostilbene compounds substituted with a nitrogen-containing heterocyclic group for example, those described in US-A-2,933,390 and US-A-3,635,721
  • aromatic organic acid-formaldehyde condensates for example, those described in US-A-3,743,510
  • cadmium salts for example, those described in US-A-3,743,510
  • cadmium salts for example, those described in US-A-3,743,510
  • cadmium salts for example, those described in US-A-3,743,510
  • cadmium salts for example, those described in US-A-3,743,510
  • azaindene compounds can be present.
  • Amultilayer natural color photographic material generally possesses at least one red-sensitive silver halide emulsion layer, at least one green-sensitive silver halide emulsion layer, and at least one blue-sensitive silver halide emulsion layer, respectively, on a support.
  • the order of these layers can be varied, if desired.
  • a cyan-forming coupler is present in a red-sensitive emulsion layer
  • a magenta-forming coupler is present in a green-sensitive emulsion layer
  • a yellow-forming coupler is present in a blue-sensitive emulsion layer, respectively.
  • different combinations can be employed.
  • A specifically represents a coupler residual group or an oxidation reduction group.
  • any known coupler residual group can be utilized. Suitable examples thereof include a yellow coupler residual group (for example, an open-chain ketomethylene type coupler residual group), a magenta coupler residual group (for example, a 5-pyrazolone type coupler residual group, a pyrazoloimidazole type coupler residual group or a pyrazolotriazole type coupler residual group), a cyan coupler residual group (for example, a phenol type coupler residual group or a naphthol type coupler residual group), and a non-color forming coupler residual group (for example, an indanone type coupler residual group or an acetophenone type coupler residual group).
  • the heterocyclic type coupler residual groups as described in for example, US-A-4,315,070, US-A-4,183,752, US-A-3,961,959and US-A-4,171,223 are also useful.
  • coupler residual groups include those represented by the general formula (Cp-1), (Cp-2), (Cp-3), (Cp-4), (Cp-5), (Cp-6), (Cp-7), (Cp-8), (Cp-9) or (Cp-10) described below. These coupler residual groups are preferred because of their high coupling rates.
  • the free bond attached to the coupling position indicates a position to which a group capable of being released upon coupling is bonded.
  • R 51 , R 52 , R 53 , R 54 , R 55 , R 56 , R 57 , R 58 , R 59 , R 69 , R 61 , R 62 or R s3 in the above-described general formulae contains a diffusion-resistant group, it is selected so that the total number of carbon atoms included therein is form 8 to 40 and preferably from 10 to 30. In other cases, the total number of carbon atoms included therein is preferably not more than 15.
  • any of the above-described substituents forms a divalent group and may connect to a repeating unit, for instance.
  • the total number of carbon atoms can be outside of the above-described range.
  • R 51 to R s3 , d and e in the above-described general formulae (Cp-1) to (Cp-10) are now explained in detail.
  • R 41 represents an aliphatic group, an aromatic group or a heterocyclic group
  • R 42 represents an aromatic group or a heterocyclic group
  • R 43 , R 44 and R 45 each represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group.
  • R 51 represents a group as defined for R 41 .
  • R 52 and R 53 each represents a group as defined for R 42 .
  • R 54 represents a group as defined for R 41 , or N ⁇ C-.
  • R 55 represents a group as defined for R 41 .
  • R 56 and R 57 each represents a group as defined for R 43 , R 41 S-, R 41 O-,
  • R 58 represents a group as defined for R 41 .
  • R 59 represents a group as defined for R 41 , R 41 O-, R 41 S-, a halogen atom or d represents an integer from 0 to 3.
  • d represents 2 or more
  • two or more R 59 's may be the same or different.
  • each of two R 59 's may be a divalent group and connected with each other to form a cyclic structure.
  • divalent groups for forming a cyclic structure include a wherein f represents an integer from 0 to 4; and g represents an integer from 0 to 2.
  • R 60 represents a group as defined for R 41 .
  • R 61 represents a group as defined for R 41 .
  • R 62 represents a group as defined for R 41 , R 41 CONH-, R 41 OCONH-, R 41 SO 2 NH-, R 43 0-, R 4i S-, a halogen atom or
  • R 63 represents a group as defined for R 41 , R 41 S0 2 -, R 41 OCO-, ROSO 2 -, a halogen atom, a nitro group, a cyano group or R 43 CO-.
  • Symbol "e” represents an integer from 0 to 4. When e represents 2 or more, two or more R 62 's or R 63 's may be the same or different.
  • the aliphatic group described above is an aliphatic group having from 1 to 32 carbon atoms, preferably from 1 to 22 carbon atoms, and may be saturated or unsaturated, straight-chain, branched chain or cyclic, or substituted or unsubstituted.
  • unsubstituted aliphatic groups include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, an isobutyl group, a tert-amyl group, a hexyl group, a cyclohexyl group, a 2-ethylhexyl group, an octyl group, a, 1,1,3,3,-tetramethylbutyl group, a decyl group, a dodecyl group, a hexadecyl group, or an octadecyl group.
  • the aromatic group described above is an aromatic group having from 6 to 20 carbon atoms, and preferably an unsubstituted or substituted phenyl group or an unsubstituted or substituted naphthyl group.
  • the heterocyclic group described above is a heterocyclic group having from 1 to 20 carbon atoms, preferably from 1 to 7 carbon atoms and containing at least one of a nitrogen atom, an oxygen atom and a sulfur atom, as a hetero atom, and preferably a three-membered to eight-membered, substituted or unsubstituted heterocyclic group.
  • unsubstituted heterocyclic group examples include a 2-pyridyl group, a 2-thienyl group, a 2-furyl group, a 1-imidazolyl group, a i-indolyl group, a phthalimido group, a 1,3,4-thiadia- zol-2-yl group, a 2-quinolyl group, a 2,4-dioxo-1,3-imidazolidin-5-yl group, a 2,4-dioxo-1,3-imidazolidine-3-yl group, a succinimido group, a 1,2,4-triazol-2-yl group, or a 1-pyrazolyl group.
  • the aliphatic group, aromatic group and heterocyclic group may have a substituent as described above.
  • substituents include a halogen atom, R 47 0-, R 46 S-, a group as defined for R 46 , R 46 COO-, R 47 OSO 2 -, a cyano group, or a nitro group.
  • R 46 represents an aliphatic group, an aromatic group or a heterocyclic group
  • R 47 , R 48 and R 49 each represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group.
  • the aliphatic group, aromatic group and heterocyclic group each has the same meaning as defined above.
  • R 51 is preferably an aliphatic group or an aromatic group.
  • R 52 , R 53 and R 55 each is preferably an aromatic group.
  • R 54 is preferably R 41 COHN- or
  • R 56 and R 57 each is preferably an aliphatic group, R 41 O- or R 41 S-.
  • R 58 is preferably an aliphatic group or an aromatic group.
  • R 59 in general formula (Cp-6) is preferably a chlorine atom, an aliphatic group or R 41 CONH-.
  • d in the general formula (CP-6) is preferably 1 or 2.
  • R 60 is preferably an aromatic group.
  • R 59 in the general formula (Cp-7) is preferably R 41 CONH-.
  • d in the general formula (Cp-7) is preferably 1.
  • R 61 is preferably an aliphatic group or an aromatic group.
  • e in the general formula (Cp-8) is preferably 0 or 1.
  • R 62 is preferably R 41 OCONH-, R 41 CONH- or R 41 SO 2 NH-.
  • the position of R 62 is preferably the 5-position of the naphthol ring.
  • R 63 in the general formula (Cp-9) is preferably R 41 CONH-, R 41 SO 2 NH-, R 41 SO 2 -, a nitro group or a cyano group.
  • R 63 in the general formula (Cp-10) is preferably R 43 OCO- or R 43 CO-.
  • R 51 to R 63 are set forth below.
  • R 51 examples include a tert-butyl group, a 4-methoxyphenyl group, a phenyl group, a 3-[2-(2,4-di-tert-amylphenoxy)butanamido]phenyl group, or a methyl group.
  • R 52 and R 53 examples include a 2-chloro-5-dodecyloxycarbonylphenyl group, a 2-chloro-5-hexadecylsulfonamidophenyl group, a 2-chloro-5-tetradecanamidophenyl group, a 2-chloro-5-[4-(2,4-di-tert-amylphenoxy)-butanamido]phenyl group, a 2-chloro-5-[2-(2,4-di-tert-amylphenoxy)butanamido]phenyl group, 2-methoxyphenyl group, a 2-methoxy-5-tetradecyloxycarbonylphenyl group, a 2-chloro-5-(1- ethoxycarbonylethoxycarbonyl)phenyl group, a 2-pyridyl group, a 2-chloro-5-octyloxycarbonyl phenyl group, a 2,4-dich
  • R 54 examples include a 3-[2-(2,4-di-tert-amylphenoxy)butanamido]benzamido group, a 3-[4-(2,4-di-tert-amylphenoxy)butanamido]benzamido group, a 2-chloro-5-tetradecanamidoanilino group, a 5-(2,4-di-tert-amylphenoxyacetamido)benzamido group, a 2-chloro-5-dodecenylsuccinimidoanilino group, a 2-chloro-5-[2-(3-tert-butyl-4-hydroxyphenoxy)tetradecanamido]anilino group, a 2,2-dimethylpropanamido group, a 2-(3-pentadecylphenoxy)-butanamido group, a pyrrolidino group, or an N,N-dibutylamino group.
  • R 55 examples include a 2,4,6-trichlorophenyl group, a 2-chlorophenyl group, a 2,5-dichlorophenyl group, a 2,3-dichlorophenyl group, a 2,6-dichloro-4-methoxyphenyl group, a 4-[2-(2,4-di-tert-amylphenoxy)butanamido]phenyl group, or a 2,6-dichloro-4-methane slfonylphenyl group.
  • R 56 examples include a methyl group, an ethyl group, an isopropyl group, a methoxy group, an ethoxy group, a methylthio group, an ethylthio group, a 3-phenylureido group, or a 3-(2,4-di-tert-amylphenoxy)propyl group.
  • R 57 examples include a 3-(2,4-di-tert-amylphenoxy)propyl group, a 3-[4- ⁇ 2-[4-(4-hydroxyphenylsulfo- nyl)phenoxy]tetradecanamido ⁇ phenyl]propyl group, a methoxy group, a methylthio group, an ethylthio group, a methyl group, a 1-methyl-2- ⁇ 2-octyloxy-5-[2-octyloxy-5-(1,1,3,3-tetramethylbutyl)phenyl-sulfonamido]-phenylsulfonamido ⁇ ethyl group, a 3-[4-(4-dodecyloxyphenylsulfonamido)phenyl]propyl group, a 1,1-dimethyl-2-[2-octyloxy-5-(1,1,3,3-tetramethylbutyl)-phenylsul
  • R 58 examples include a 2-chlorophenyl group, a pentafluorophenyl group, a heptafluoropropyl group, a 1-(2,4-di-tert-amylphenoxy)propyl group, a 3-(2,4-di-tert-amylphenoxy)propyl group, a 2,4-di-tert-amylphenoxymethyl group, or a furyl group.
  • R 59 examples include a chlorine atom, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, a 2-(2,4-di-tert-amylphenoxy)butanamido group, a 2-(2,4-di-tert-amylphenoxy)hexanami- do group, a 2-(2,4-di-tert-octylphenoxy)octanamido group, a 2-(2-chlorophenoxy)tetradecanamido group, a 2-[4-(4-hydroxyphenylsulfonyl)phenoxy]tetradecanamido group, or a 2-[2-(2,4-di-tert-amylphenoxyacetamido)phenoxy]butanamido group.
  • R 60 examples include a 4-cyanophenyl group, 2-cyanophenyl group, a 4-butylsulfonylphenyl group, a 4-propylsulfonylphenyl group, a 4-chloro-3-cyanophenyl group, a 4-ethoxycarbonylphenyl group, or a 3,4-dichlorophenyl group.
  • R s1 examples include a dodecyl group, a hexadecyl group, a cyclohexyl group, a 3-(2,4-di-tert-amyl- phenoxy)propyl group, a 4-(2,4-di-tert-amylphenoxy)butyl group, a 3-dodecyloxypropyl group, a tert-butyl group, a 2-methoxy-5-dodecyloxycarbonylphenyl group, or a 1-naphthyl group.
  • R 62 examples include an isobutyloxycarbonylamino group, an ethoxycarbonylamino group, a phenyl- sulfonylamino group, a methanesulfonamido group, a benzamido group, a trifluoroacetamido group, a 3-phenylureido group, a butoxycarbonylamino group, or an acetamido group.
  • R 63 examples include a 2,4-di-tert-amylphenoxyacetamido group, a 2-(2,4-di-tert-amylphenoxy)butanamido group, a hexadecylsulfonamido group, an N-methyl-N-octadecylsulfamoyl group, an N,N-dioctylsulfa- moyl group, a 4-tert-octylbenzoyl group, a dodecyloxycarbonyl group, a chlorine atom, a nitro group, a cyano group, an N-[4-(2,4-di-tert-amylphemoxy)butyl]carbomoyl group, an N-3-(2,4-di-tert-amylphenoxy)propylsulfamoyl group, a methanesulfonyl group, or a he
  • A represents an oxidation reduction group in the general formula (I)
  • the group is specifically represented by the following general formula (II): wherein P and Q each represents an oxygen atom or a substituted or unsubstituted imino group; at least one of the n X and Y's represents a methine group having the group -(L 1 ) a -(L 2 ) b -Z as a substituent, and other X and Y's which are not such a substituent each represents a substituted or unsubstituted methine group or a nitrogen atom; n represents an integer from 1 to 3 (n X's and n Y's may be the same or different); A 1 and A 2 each represents a hydrogen atom or a group capable of being eliminated with an alkali; or any two substituents of P, X, Y, Q, A 1 and A 2 may be divalent groups and connected with each other to form a cyclic structure.
  • P and Q each
  • P and Q each represents a substituted or unsubstituted imino group
  • an imino group substituted with a sulfonyl group or an acyl group is preferred.
  • P and Q each preferably represents an oxygen atom or a group represented by general formula (N-1).
  • a 1 and A 2 each represents a group capable of being eliminated with an alkali (hereinafter referred to as a precursor group)
  • preferred examples of the precursor groups include a hydrolyzable group, for example, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group and a sulfonyl group; a precursor group of the type utilizing a reverse Michael reaction as described in US-A-4,009,029; a precursor group of the type utilizing an anion generated after a ring cleavage reaction as the intramolecular nucleophilic group as described in US-A-4,310,612; a precursor group utilizing the electron transfer of an anion via a conjugated system whereby a cleavage reaction occurs as described in US-A-3,674,478, US-A-3,932,480 and US-A-3,993,661; a precursor group utilizing the electron transfer of an anion reacted after a ring
  • P represents an oxygen atom and A 2 represents a hydrogen atom.
  • X and Y each represents a substituted or unsubstituted methine group other than when X or Y represents a methine group having a group of -(L 1 ) a -(L 2 ) b -Z as a substituent.
  • Examples of the cyclic structures formed by condensing the benzene ring and another ring include a naphthalene ring, a benzonorbornene ring, a chroman ring, an indole ring, a benzothiophene ring, a quinoline ring, a benzofuran ring, a 2,3-dihydrobenzofuran ring, an indane ring and an indene ring. These rings may further have one or more substituents.
  • R 64 and the substituents on the condensed ring described above include R 41 , a halogen atom, R 43 0-, R 43 S-, a cyano group, or wherein R 41 , R 43 , R 44 and R 45 each has the same meaning as defined above.
  • substituents represented by R 64 include a methyl group, an ethyl group, a tert-butyl group, a methoxy group, a methylthio group, dodecylthio group, a 3-(2,4-di-tert-amylphenoxy)pro- pylthio group, an N-3-(2,4-di-tert-amylphenoxy)propylcarbamoyl group, an N-methyl-N-octadecyloxycarba- moyl group, a methoxycarbonyl group, a dodecyloxycarbonyl group, a propylcarbomoyl group, a hydroxyl group, or an N,N-diotylcarbamoyl group.
  • Representative examples of the cyclic structure formed by connecting with two R 64 's includes a group represented by the following formula:
  • P and Q each preferably represents an oxygen atom.
  • a 1 and A 2 each preferably represents a hydrogen atom.
  • the groups represented by L 1 and L 2 may or may not be used in the present invention. It is preferred not to use the groups represented by L 1 and L 2 . When used, an appropriate group can be selected depending on the purpose. When L 1 and L 2 represents a timing group, suitable examples thereof include known linking groups described below.
  • T-1 general formula (T-1): wherein the bond indicated by * denotes the position at which the group is connected to the left side group in general formula (I); the bond indicated by ** denotes the position at which the group is connected to the right side group in general formula (I); W represents an oxygen atom, a sulfur atom or R 65 and R 66 each represents a hydrogen atom or a substituent; R 67 represents a substituent; t represents 1 or 2; and when t represents 2, two may be the same or different.
  • T-1 general formula (T-1): wherein the bond indicated by * denotes the position at which the group is connected to the left side group in general formula (I); the bond indicated by ** denotes the position at which the group is connected to the right side group in general formula (I); W represents an oxygen atom, a sulfur atom or R 65 and R 66 each represents a hydrogen atom or a substituent; R 67 represents a substituent; t represents 1 or 2; and when t represents 2, two may be the same or
  • R 65 , R ss , or R 67 include R 69 , R 69 CO-, R 69 SO 2 -, wherein R 69 has the same meaning as defined for R 41 above; and R 70 has the same meaning as defined for R 43 above.
  • Each of the groups represented by R 65 ,R 66 and R 67 may also represent a divalent group connected with each other to form a cyclic structure.
  • T-2 the timing groups as described in US-A-4,248,962 and are represented by the following general formula (T-2): wherein the bond indicated by * denotes the position at which the group is connected to the left side group in the general formula (I); the bond indicated by ** denotes the position at which the group is connected to the right side group in the general formula (I); Nu represents a nucleophilic group including, e.g., an oxygen atom or a sulfur atom; E represents an electrophilic group which is able to cleave the bond indicated by ** upon a nucleophilic attack of Nu; and Link represents a linking group which connects Nu with E in a stereochemical position capable of causing an intramolecular nucleophilic displacement reaction between Nu and E.
  • T-2 the bond indicated by * denotes the position at which the group is connected to the left side group in the general formula (I)
  • the bond indicated by ** denotes the position at which the group is connected to the right side group in the general formula (I)
  • Nu represents
  • T-3 wherein the bond indicated by *, the bond indicated by **, W, R 65 , R 66 and t each has the same meaning as defined in the general formula (T-1) above.
  • Examples of these groups include, for example, those as described in DE-A-2,626,315 and are represented by the following formula (T-4) or (T-5): wherein the bond indicated by * and the bond indicated by ** each has the same meaning as defined in the general formula (T-1) above.
  • L 1 represents a group capable of cleaving (L 2 )b-Z upon a reaction with an oxidation product of a developing agent after being cleaved from A
  • the group is specifically a group capable of forming a coupler after being cleaved from A or a group capable of forming an oxidation reduction group after being cleaved from A.
  • L 2 represents a group capable of cleaving Z upon a reaction with an oxidation product of a developing agent after being cleaved from A-(L 1 )a
  • the group is specifically a group capable of forming a coupler after being cleaved from A-(L 1 )a or a group capable of forming an oxidation reduction group after being cleaved from A-(L 1 )a.
  • Examples of the group forming a coupler include a group which is formed by eliminating a hydrogen atom from a hydroxy group of a phenol type coupler and is connected to A- or A-(L 1 )a- at the oxygen atom of the hydroxy group, and a group which is formed by eliminating a hydrogen atom from a hydroxy group of a 5-hy- droxypyrazole which is a tautomer of a 5-pyrazolone type coupler and is connected to A- or A-(L 1 )a- at the oxygen atom of the hydroxy group.
  • the group forms a phenol type coupler or a 5-pyrazolone type coupler for the first time after being released from A- or A-(L 1 )a-.
  • These couplers have (L 2 )b-Z or Z at their coupling position.
  • L 1 or L 2 represents a group capable of forming a coupler after being released from A- or A-(L 1 )a
  • the group is preferably represented by the following general formula (V), (VI), (VII) or (VIII): wherein the bond indicated by * denotes the position at which the group is connected to the left side group in the general formula (I); the bond indicated by ** denotes the position at which the group is connected to the right side group in the general formula (I):
  • V 1 and V 2 each represents a substituent;
  • V 3 , V 4 , V 5 and V 6 each represents a nitrogen atom or a substituted or unsubstituted methine group;
  • V 7 represents a substituent;
  • X represents an integerfrom 0 to 4, when X represents 2 or more, two ore more V 7 's may be the same or different, or two V 7 's may be connected with each other to form a cyclic structure;
  • V 8 represents CO-, -SO 2
  • V 1 preferably represents R 71 .
  • V 2 preferably represents R 72 , R 72 CO-, R 72 SO 2 -, R 72 S-, R 72 0- or
  • Suitable examples of the ring structure formed by connecting V 1 with V 2 include an indene ring, an indole ring, a pyrazole ring and a benzothiophene ring.
  • V 3 , V 4 , V 5 or V 6 represents a substituted methine group
  • examples of preferred substituents include R 71 , R 73 0-, R 71 S- and R 71 CONH-.
  • V 7 preferably represents a halogen atom, R 71' R 71 CONH-, R 71 SO 2 NH-, R 73 0- R 71 S-, R 71 CO- and R 73 00C-.
  • Suitable examples of the ring structure formed by connecting plural V 7 's with each other include a naphthalene ring, a quinoline ring, an oxyindole ring, a benzodiazepin-2,4-dione ring, a benzimidazol-2-one ring and a benzothiophene ring.
  • V 8 represents a substituted imino group
  • a preferred group is a group of R 73 - .
  • Preferred ring structures formed by V 9 together with include an indole ring, imidazolinone ring, a 1,2,5-thiadiozolin-1,1-dioxide ring, a 3-pyrazolin-5-one ring, a 3-isooxazolin-5-one ring and
  • V 10 include R 73 , R 73 0-, and R 71 S-.
  • R 71 and R 72 each represents an aliphatic group, an aromatic group or a heterocyclic group
  • R 73 , R 74 and R 75 each represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group.
  • the aliphatic group, aromatic group and heterocyclic group each has the same meaning as defined for R 41 above, but the total number of carbon atoms included therein is preferably not more than 10.
  • the group represented by L 1 or L 2 is a group capable of forming an oxidation reduction group after being released from A- or A-(L 1 ) a
  • the group is preferably represented by the following general formula (IX): wherein the bond indicated by * denotes the position at which the group is connected to the left side group in general formula (I); A2', P', Q' and n' are as A 2 , P, Q and n defined in general formula (II); at least one of the n' X' and Y's represents a methine group having the group -(L 2 )b-Z or -Z as in general formula (I) as a substituent, and other X' and Y's each represents a substituted or unsubstituted methine group ora a nitrogen atom; or any two substituents of A2', P', Q', X' and Y' may be divalent groups connected with each other to form a cyclic structure
  • Suitable examples of the cyclic structure include a benzene ring or a pyridine ring.
  • Q' represents an oxygen atom
  • R 76 has the same meaning as R64 defined in the general formula (III) or (IV); and y represents an integer from 0 to 3, and when y represents 2 or more, two or more R 76 's may be the same or different, or two R 76 's may be connected with each other to form a cyclic structure.
  • substituents represented by R 76 include an alkoxy group (for example, methoxy, ethoxy), an acylamino group (for example, acetamido, benzamido), a sulfonamido group (for example, methanesulfonamido, benzenesulfonamido), an alkylthio group (for example, methylthio, ethylthio), a carbamoyl group (for example, N-propylcarbamoyl, N-tert-butylcarbamoyl, N-isopropylcarbamoyl), an alkoxycarbonyl group (for example, methoxycarbonyl, propoxycarbonyl), an aliphatic group (for example, methyl, tert-butyl), a halogen atom (for example, fluorine, chlorine), a sulfamoyl group (for example, N-propyl), an acyla
  • Representative examples of the cyclic structure formed by connecting with two R 76 's includes a group represented by the following formula: wherein the bond indicated by * and the bond indicated by** each has the same meaning as defined in the general formula (XI) above.
  • the group represented by Z is a group represented by formula (XII), (XIII) or (XIV). It is preferred that the group Z is connected to A-(L 1 ) a -(L 2 ) b - in the general formula (I) through a hetero atom which can be substituted present in its molecule.
  • R 33 , R34 and R 35 each represents an aliphatic group
  • the aliphatic group has from 1 to 5 carbon atoms.
  • the aliphatic group represented by R 31 , R 32 , R 33 , R 34 or R 35 may be a straight chain, branched chain or cyclic, saturated or unsaturated, or substituted or unsubstituted aliphatic group.
  • substituents for the aliphatic group include, for example, a halogen atom (for example, fluorine, chlorine, bromine), an alkoxy group (for example, methoxy, ethoxy), and an alkylthio group (for example, methylthio, ethylthio).
  • the aromatic group represented by X 2 or R 32 may be substituted. Suitable examples of the substituent(s) include those as illustrated for the aliphatic group above.
  • the heterocyclic group represented by X 3 or R 32 may be a saturated or unsaturated, or substituted or unsubstituted heterocylic group containing an oxygen atom, a sulfur atom or a nitrogen atom as a hetero atom and include, for example, a pyridine ring, an imidazole ring, a piperidine ring, an oxirane ring, a sulfolane ring, an imidazolidine ring, a thiazepine ring and a pyrazole ring.
  • Suitable example of the substituents include these as illustrated for the aliphatic group above.
  • the compound represented by the general formula (I) according to the present invention includes these where the compound is a bis compound, a telomer, or a polymer.
  • the compound in the case of a polymer, the compound may be a polymer derived from a monomer represented by the general formula (XV) described below and having a recurring unit represented by the general formula (XVI) described below or may be a copolymer of the above described monomer and at least one non-color forming monomer containing at least one ethylene group which does not have the ability of coupling with an oxidation product of an aromatic primary amine developing agent.
  • two or more kinds of the monomer represented by the general formula (XV) may be simultaneously polymerized.
  • R represents a hydrogen atom, a lower alkyl group having from 1 to 4 carbon atoms or a chlorine atom; All represents -CONH-, -NHCONH-, -NHCOO-, -COO-, -SO 2 -, -CO-, -NHCO-, -S0 2 NH-, -NHS0 2 -, - OCO-, -OCONH-, -NH- or -0-; A12 represents -CONH- or -COO-; A 13 represents a substituted or unsubstituted alkylene group having from 1 to 10 carbon atoms, a substituted or unsubstituted aralkylene group, or a substituted or unsubstituted arylene group.
  • the alkylene group may be a straight chain or branched chain alkylene group.
  • Suitable examples of the alkylene group include a methylene group, a methylmethylene group, a dimethylmethylene group, a dimethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group and a decylmethylene group.
  • Suitable examples of the aralkylene group include a benzilidene group.
  • Suitable examples of the arylene group include a phenylene group and a naphthylene group.
  • QQ in the above described general formulae represents a residue of the compound represented by general formula (I) and may be bonded through any moiety of the substituents described above except of the substituent represented by Z.
  • i, j, and k each represents 0 or 1 excluding the case that i, j, and k are simultaneously 0.
  • Examples of the substituent for the alkylene group, aralkylene group or arylene group represented by A 13 include an aryl group (for example, phenyl), a nitro group, a hydroxy group, a cyano group, a sulfo group, an alkoxy group (for example, methoxy), an aryloxy group (for example, phenoxy), an acyloxy group (for example, acetoxy), an acylamino group (for example, acetylamino), a sulfonamido group (for example, methanesulfonamido), a sulfamoyl group (for example, methylsulfamoyl), a halogen atom (for example, fluorine, chlorine, or bromine), a carboxy group, a carbomoyl group (for example, methylcarbamoyl), an alkoxycarbonyl group (for example, methoxycarbonyl) and a
  • non-color forming ethylenic monomer which does not cause coupling with the oxidation product of an aromatic primary amine developing agent
  • an acrylic acid such as, e.g., acrylic acid, a-chloroacrylic acid and a-alkylacrylic acid, an ester or amide derived from an acrylic acid, a methylenebisacrylamide, a vinyl ester, an acrylonitrile, an aromatic vinyl compound, a maleic acid derivative and a vinylpyridine.
  • an acrylic acid such as, e.g., acrylic acid, a-chloroacrylic acid and a-alkylacrylic acid
  • an ester or amide derived from an acrylic acid e.g., a methylenebisacrylamide, a vinyl ester, an acrylonitrile, an aromatic vinyl compound, a maleic acid derivative and a vinylpyridine.
  • two or more of such non-color forming ethylenically unsaturated monomers can be used together.
  • any two groups represented by A, L 1' L 2 , and Z may have a bond in addition to the bond represented in general formula (I) and may be connected with each other. In such cases, even when the second bond is not cleaved at the time of development, the effect of the present invention can be achieved.
  • Examples of compounds including such second bond are represented by the following general formula: wherein A, L 1' L 2 , a and b each has the same meaning as defined in general formula (I) above.
  • Particularly preferred examples of the above described compounds include these represented by the following general formula (XVII): wherein L 2 , b, Z, R 58 and R 59 each has the same meaning as earlier defined; h and V each represents 0 or 1; and A 14 represents a divalent organic group necessary to form a 5-membered to 8-membered ring.
  • divalent group represented by A 14 examples include -O-CH , and -S-CH .
  • the compounds capable of releasing a bleach accelerating agent used in the present invention can be easily prepared according to the descriptions of the patent specifications mentioned above.
  • the amount of the compound capable of releasing a bleach accelerating agent according to the present invention added to the photographic light-sensitive material is preferably from 1x10 -7 mol to 1x10 -10 mol, particularly preferably from 1x10- s to 5x10- 2 mol, per m 2 of the photographic light-sensitive material.
  • the compound capable of releasing a bleach accelerating agent according to the present invention can be added to any layer of the photographic light-sensitive material, but preferably to a light-sensitive emulsion layer. Adding the compound to more light-sensitive emulsion layers leads to more remarkable effects of the present invention.
  • any of silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodobromide, silver chloride and silver chloroiodide may be used as the silver halide other than the silver halide emulsion according to the present invention.
  • a particularly preferred silver halide is silver iodobromide.
  • Silver halide grains in the photographic emulsion may have a regular crystal structure, for example, a cubic, octahedral or tetradecahedral structure, an irregular crystal structure, for example, a spherical structure, a crystal defect, for example, a twin plane , or a composite structure thereof. Further, a mixture of grains having various crystal structures may be employed.
  • the silver halide emulsion may be a monodispersed emulsion having a narrow grain size distribution or a polydispersed emulsion having a broad grain size distribution.
  • tabular silver halide grains such as those having an aspect ratio of 5 or more can be employed in the emulsion layers.
  • the crystal structure of the silver halide grains used in the emulsion layers may be uniform, composed of different halide compositions between the inner portion and the outer portion, or may have a stratified structure. Examples of such emulsion grains are described, for example, in GB-B-1,047,146, US-A-3,505,068 and US-A-4,444,877, and JP-A-58-248469.
  • silver halide emulsions in which silver halide grains having different compositions are connected upon epitaxial junctions or silver halide emulsions in which silver halide grains are connected with compounds other than silver halide such as, e.g., silver thiocyanate and lead oxide may also be employed.
  • either grains in which latent images are formed mainly on the surface thereof or internal latent image type grains in which latent images are formed mainly in the interior thereof can be employed. Further, silver halide grains whose interior has been chemically sensitized may be employed.
  • the silver halide photographic emulsion used in the present invention can be prepared using appropriately known methods, for example, those as described in Research Disclosure, Vol. 176, No. 17643 (December 1978), page 22 to 23, "I. Emulsion Preparation and Types" and ibid., Vol. 187, No. 18716 (November 1979), page 658.
  • various silver halide solvents for example, ammonia, potassium thiocyanate, and thioethers and thione compounds as described in US-A-3,271,157, JP-A-51-12360, JP-A-53-82408, JP-A-53-144319, JP-A-54-100717 and JP-1-54-155828 can be used.
  • Representative monodispersed emulsions are those comprising silver halide grains having an average grain diameter of about 0.1 f..lm or more and at least about 95% by weight of the total silver halide grains have a diameter within the range of ⁇ 40% of the average grain diameter.
  • a monodispersed emulsion comprising silver halide grains having an average grain diameter of from about 0.25 ⁇ m to 2 ⁇ m and at least about 95% by weight or by number of particles of the total silver halide grains have a diameter within the range of ⁇ 20% of the average grain diameter.
  • the silver halide grains e.g., cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts thereof, rhodium salts or complex salts thereof, iron salts or complex salts thereof may be present.
  • the photographic emulsions used in the present invention are usually subject to, after physical ripening, chemical ripening and spectral sensitization.
  • Various kinds of additives which can be employed in these steps are described, for example, in Research Disclosure, No. 18743 (December 1978) and ibid., No. 18716 (November 1979) as mentioned above and relevant parts thereof are summarized in the table shown below.
  • various known spectral sensitizers can be employed together, as well as the above described spectral sensitizers.
  • various color couplers can be employed and specific examples thereof are described, for example, in the patents cited in Research Disclosure, No. 18743, "VII-C” to “VII-G” as mentioned above.
  • dye forming couplers couplers capable of providing the three primary colors (i.e., yellow, magenta and cyan) in a subtractive process upon color development are important.
  • Specific examples of preferred diffusion-resistant, four-equivalent or two-equivalent couplers are described in the patents cited in Research Disclosure, No. 17643, "VII-C” and “VII-D” as mentioned above.
  • couplers as described below are preferably employed in the present invention.
  • a-Pivaloyla- cetanilide type couplers are characterized by excellent fastness, particularly light fastness, of the dyes formed, and the a-benzoylacetanilide type couplers are characterized by providing high color density.
  • hydrophobic 5-pyrazolone type couplers and pyrazoloazole type couplers each having a ballast group may be employed.
  • those substituted with an arylamino group or an acylamino group at the 3-position thereof are preferred in view of hue and color density of dyes formed therefrom.
  • cyan couplers used in the present invention hydrophobic and diffusion-resistant naphthol type and phenol type couplers can be exemplified. Typical examples preferably include oxygen atom releasing type two-equivalent naphthol type couplers.
  • Cyan couplers capable of forming cyan dyes fast to humidity and temperature are preferably used in the present invention.
  • Typical examples thereof include the phenol type cyan couplers having an alkyl group higher than a methyl group at the meta-position of the phenol nucleus as described in US-A-3,772,002, 2,5-diacylamino-substituted phenol type couplers, phenol type couplers having a phenolureido group at the 2-position thereof and an acylamino group at the 5-position thereof, and 5-aminonaphthol type cyan couplers as described in EP-A-161,626.
  • couplers capable of forming appropriately diffusible dyes can be used together in order to improve graininess.
  • Specific examples of such types of magenta couplers are described, for example, in US-A-4,336,237, and those of yellow, magenta and cyan couplers are described, for example, in EP-B-96,570.
  • Dye forming couplers and special couplers as described above may form polymers including dimers or more.
  • Typical examples of polymer dye forming couplers are described, for example, in US-A-3,451,820.
  • Specific examples of polymer magenta couplers are described, for example, in US-A-4,367,282.
  • Couplers capable of releasing a photographically useful group during the course of coupling can also be employed preferably in the present invention.
  • Specific examples of useful DIR couplers capable of releasing a development inhibitor are described, for example, in the patents cited in Research Disclosure, NO. 17643, "VII-F" described above.
  • a DIR coupler is a compound which can release a development inhibitor releasing compound upon reaction with the oxidation product of the developing agent during development.
  • the development inhibitor is adsorbed on the silver, which causes to retard the desilvering.
  • a photographic material of the present invention further uses the DIR coupler represented by formula (Y).
  • A denotes a coupler radical group which eliminates by means of the coupling reaction with the oxidation product of the primary aromatic amine developing agent
  • TIME denotes a timing group which bonds to the active coupling position in A and which releases B after separation from A due to the coupling reaction
  • B denotes a group represented by general formulae (Ila), (IIb), (IIc), (lid), (lie), (Ilf), (IIg), (IIh), (Ili), (IIj), (Ilk), (lIf), (IIm), (IIn), (IIo), or (lip) mentioned below
  • n denotes an integer equal to 0 or 1, with the condition that when n is 0, B is directly bonded to A.
  • X 1 is chosen from a substituted or unsubstituted aliphatic group with 1 to 4 carbon atoms (the substituent group is chosen from an alkoxy group, an alkoxycarbonyl group, a hydroxyl group, an acylamine group, a carbamoyl group, a sulfonyl group, a sulfonamido group, a sulfamoyl group, an amino group, an acyloxy group, a cyano group, a ureido group, an acyl group, a halogen atom, or an alkylthio group.
  • the substituent group is chosen from an alkoxy group, an alkoxycarbonyl group, a hydroxyl group, an acylamine group, a carbamoyl group, a sulfonyl group, a sulfonamido group, a sulfamoyl group, an amino group, an acyloxy group,
  • the number of carbon atoms contained in this substituent group is 3 or less), or a substituted phenyl group (the substituent group is chosen from a hydroxyl group, an alkoxycarbonyl group, an acylamino group, a carbamoyl group, a sulfonyl group, a sulfonamido group, a sulfamoyl group, an acyloxy group, a ureido group, a carboxyl group, a cyano group, a nitro group, an amino group, or an acyl group.
  • the carbon atoms contained in such substituted group number is 3 or less).
  • X 2 denotes a hydrogen atom, an aliphatic group, a halogen atom, a hydroxyl group, an alkoxy group, an alkylthio group, an alkoxycarbonyl group, an acylamino group, a carbamoyl group, a sulfonyl group, a sulfonamido group, a sulfamoyl group, an acyloxy group, a ureido group, a cyano group, a nitro group, an amino group, an alkoxycarbonylamino group, an aryloxycarbonyl group or an acyl group;
  • X 3 is an oxygen atom, a sulfur atom, or an imino group with 4 or less carbon atoms, and m denotes an integer equal to 1 or 2, with the proviso that the number m of carbon atoms contained in X 2 is 8 or less, and when m is 2, two X 2 groups may be the same
  • Coupler residual groups which form dyes (for example, yellow, magenta, cyan) by means of a coupling reaction with the oxidized form of the primary aromatic amine developer, and coupler radicals which give coupling reactants with essentially no absorption in the visible light region are included as the coupler radicals represented by A in general formula (Y).
  • the yellow color image forming coupling radical denoted by A there may be mentioned the pivaloyla- cetanilide group, benzoylacetanilide group, malonic acid diester group, malondiamide group, dibenzoylme- thane group, benzothiazolylacetamide group, malonic acid ester monoamide group, benzothiazolyl acetate group, benzoxazolylacetamide group, benzoxazolyl acetate malonic acid diester group, benzimidazolylaceta- mide group, or benzimidazolyl acetate groups as coupler radicals, coupler radicals derived from hetero ring-substituted acetamide or hetero ring-substituted acetate as in US-A-3,841,880, or coupler radicals derived from acylacetamides as in US-A-3,770,446, GB-B-1,459,171, DE-A-2503099, JP-A-50-139738, or
  • Coupler radicals which possess a 5-oxo-2-pyrazoline nucleus, a pyrazolo[1,5-a]benzimidazole nucleus, a pyrazoloimidazole nucleus, a pyrazolotriazole nucleus, a pyrazolotetrazole nucleus, or a cyanoacetophenone- based coupler radical are preferred as the magenta color image forming coupler radical represented by A.
  • Coupler radicals which possess a phenol nucleus or an a-naphthol nucleus are preferred as the cyan color image forming coupler represented by A.
  • coupler radicals As the form of coupler radical denoted by A there may be mentioned the coupler radicals reported in, for example, US-A-4,052,213, US-A-4,088,491, US-A-3,632,345, US-A-3,958,993, and US-A-3,961,959.
  • Examples of X 1 are a methyl group, an ethyl group, a propyl group, a butyl group, a methoxyethyl group, an ethoxyethyl group, an isobutyl group, an allyl group, a dimethylaminoethyl group, a propargyl group, a chloroethyl group, a methoxycarbonylmethyl group, a methylthioethyl group, a 4-hydroxyphenyl group, a 3-hydroxyphenyl group, a 4-sulfamoylphenyl group, a 3-sulfamoylphenyl group, a 4-carbamoylphenyl group, a 3-carbamoylphenyl group, a 4-dimethylaminophenyl group, a 3-acetamidophenyl group, a 4-propanamidophenyl group, a 4-methoxyphenyl group, a 2-
  • the couplers according to the present invention are generally used in a mixture with the principal coupler.
  • the couplers employed in the present invention are added in a proportion of 0.1 mol% to 100 mol%, and preferably 1 mol% to 50 mol%.
  • the amount of the couplers utilized with respect to the silver halide is 0.01 mol% to 20 mol%, preferably 0.5 mol% to 10 mol%, with respect to the silver halide present in the same layer or in an adjacent layer.
  • a in general formula (Y) is a coupler radical denoted by the following general formulae (Cq-1), (Cq-2), (Cq-3), (Cq-4), (Cq-5), (Cq-6), (Cq-7), (Cq-8), (Cq-9), (Cq-10), or (Cq-11).
  • These couplers, having a high coupling rate, are preferable.
  • the free bonds derived from the coupling position denote bonding positions of coupling elimination groups.
  • R 5 ,, R 52 , R 53 , R 54 R 55 , R 56 , R 57 , R 58 , R 59 , R 60 or R 61 . contain groups which are fast to diffusion, the total number of carbon atoms is selected to be 8 to 32, and preferably 10 to 22; in other cases, the total number of carbon atoms is preferably 15 or less.
  • R 51 denotes an aliphatic group, an aromatic group, an alkoxy group or a heterocyclic group
  • R 52 and R 53 denote respectively aromatic groups or heterocyclic groups.
  • the aliphatic groups denoted by R 51 preferably have 1 to 22 carbon atoms, and may be substituted or unsubstituted, linear or cyclic.
  • the preferred substituent groups for the alkyl group are an alkoxy group, an amino group, an acylamino group and a halogen atom; and these may themselves have substituents.
  • R 51 Specific examples of useful aliphatic groups for R 51 are as follows: an isopropyl group, an isobutyl group, a tert-butyl group, an isoamyl group, a tert-amyl group, a 1,1-dimethylbutyl group, a 1,1-dimethylhexyl group, a 1,1-diethylhexyl group, a dodecyl group, a hexadecyl group, an octadecyl group, a cyclohexyl group, a 2-me- thoxyisopropyl group, a 2-phenoxyisopropyl group, a 2-p-tert-butylphenoxyisopropyl group, an a-aminoisopropyl group, an a-(diethylamino)isopropyl group, an a-(succinimido)isopropyl group, an a-(phthal
  • R 5 ,, R 52 or R 53 represents aromatic groups (particularly phenyl groups)
  • the aromatic group may be substituted.
  • Phenyl and other such aromatic groups may be substituted with an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an alkoxycarbonylamino group, an aliphatic amido group, an alkylsulfamoyl group, an alkylsulfonamido group, an alkylureido group, an alkyl-substituted succinimido group, or other such group having up to 32 carbon atoms; in these cases, the alkyl group may also have a phenylene or similar aromatic group interposed in the chain.
  • the phenyl group may also be substituted with, e.g., an aryloxy group, an aryloxycarbonyl group, an arylcarbamoyl group, an arylamido group, an arylsulfamoyl group, an arylsulfonamido group and an arylureido group; the aryl group moiety of these substituent groups may also be substituted with one or more alkyl groups having a total number of 1 to 22 carbon atoms.
  • the phenyl group denoted by R 5 ,, R 52 or R 53 may also be substituted by a lower alkyl group having 1 to 6 carbon atoms also containing a substituent amino group, hydroxy group, carboxy group, sulfo group, nitro group, cyano group, thiocyano group or halogen atom.
  • R 51 , R 52 or R 53 may denote a phenyl group substituted with another condensed ring, for example, a naphthyl group, a quinolyl group, an isoquinolyl group, a chromanil group, a coumaranyl group or a tetrahydronaphthyl group. These substituent groups may themselves possess substituent groups.
  • R 51 denotes an alkoxy group
  • its alkyl moiety may also represent a straight chain or branched chain alkyl group, alkenyl group, cycloalkyl group or cycloalkenyl group with 1 to 32, preferably 1 to 22, carbon atoms, and these may be substituted with, e.g., a halogen atom, an aryl group or an alkoxy group.
  • R 51 , R 52 or R 53 denotes a heterocyclic group
  • a carbon atom of a carbonyl group of an acyl group in an a-acylacetamido, or a nitrogen atom of an amido group may be bonded via one of the ring- forming carbon atoms to the respective heterocyclic group.
  • this kind of heterocyclic group are thiophene, furan, pyran, pyrrole, pyrazole, pyridine, pyrazine, pyrimidine, pyridazine, indolizine, imidazole, thiazole, oxazole, triazine, thiadiazine and oxazine. These may furthermore possess substituent groups.
  • R 55 in general formula (Cq-3) denotes a straight chain or branched chain alkyl group with 1 to 32, preferably 1 to 22, carbon atoms (e.g., methyl, isopropyl, tert-butyl, hexyl, dodecyl), an alkenyl group (e.g., allyl), a cycloalkyl group (e.g., cyclopentyl, cyclohexyl, norbornyl), an aralkyl group (e.g., benzyl, (3-phenylethyl), a cycloalkenyl group (e.g., cyclopentenyl, cyclohexenyl); these may also be substituted with, e.g., a halogen atom, a nitro group, a cyano group, an aryl group, an alkoxy group, an aryloxy group, a carboxy group, an alkylthio- carbony
  • R 55 may also denote an aryl group (e.g., phenyl, a- or (3-naphthyl).
  • the aryl group may also possess one or more substituent groups, for example, it may possess an alkyl group, an alkenyl group, a cycloalkyl group, an aralkyl group, a cycloalkenyl group, a halogen atom, a nitro group, a cyano group, an aryl group, an alkoxy group, an aryloxy group, a carboxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfo group, a sulfamoyl group, a carbamoyl group, an acylamino group, a diacylamino group, a ureido group, a urethane group, a sulfonamido group, a heterocyclic group, an aryl
  • R 55 may denote a heterocyclic group (forexample, a 5-membered or6-membered hetero ring containing a nitrogen atom, an oxygen atom, a sulfur atom as the hetero atom, a condensed heterocyclic group, a pyridyl group, a quinolyl group, a furyl group, a benzothiazolyl group, an oxazolyl group, an imidazolyl group, a naphthoxazolyl group), a heterocyclic group substituted by means of the substituent groups enumerated with reference to the above-mentioned aryl groups, an aliphatic or aromatic acyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkylcarbamoyl group, an arylcarbamoyl group, an alkylthiocarbamoyl group or an ar- ylthiocarbamoyl group
  • R 54 denotes any of a hydrogen atom, a straight chain or branched chain alkyl or alkenyl group of 1 to 32, preferably 1 to 22, carbon atoms, a cycloalkyl group, an aralkyl group, a cycloalkenyl group (these groups may possess substituents as enumerated above with reference to R 55 ), aryl groups and heterocyclic groups (these groups may possess substituents as enumerated above with reference to R 55 ), an alkoxycarbonyl group (e.g., methoxycarbonyl, ethoxycarbonyl, stearyloxycarbonyl), an aryloxycarbonyl group (e.g., phenoxycarbonyl, naphthoxycarbonyl), an aralkyloxycarbonyl group (e.g., benzyloxycarbonyl), an alkoxy group (e.g., methoxy, ethoxy, heptadecyloxy), a
  • R 56 denotes a straight chain or branched chain alkyl group, an alkenyl group with 1 to 32, preferably 1 to 22, carbon atoms, a cycloalkyl group, an aralkyl group, or a cycloalkenyl group, and these may possess substituents as enumerated above with reference to R 55 .
  • R 56 may denote an aryl group or a heterocyclic group, and these may possess substituents as enumerated above with reference to R 55 .
  • R 56 may denote a cyano group, an alkoxy group, an aryloxy group, a halogen atom, a carboxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, a sulfo group, a sulfamoyl group, an acylamino group, a diacylamino group, a ureido group, a urethane group, a sulfonamido group, an arylsulfonyl group, an alkylsulfonyl group, an arylthio group, an alkylthio group, an alkylamino group, a dialkylamino group, an anilino group, an N-arylanilino group, an N-alkylanilino group, an N-acylanilino group, or a hydroxyl group.
  • R 57 , R 58 and R 59 denote groups used in the usual 4-equivalent form phenol or a-naphthol couplers; more specifically R 57 includes a hydrogen atom, a halogen atom, an alkoxycarbonylamino group, an aliphatic hydrocarbon radical, an N-arylureido group, an acylamino group, -0-R s2 or -S-R 62 (where R 62 is an aliphatic hydrocarbon radical); where two or more R 57 exist in the same molecule, two R 57 may be different groups, and the aliphatic hydrocarbon radical may contain substituents.
  • the aryl group may possess the substituents enumerated with reference to R 55 above.
  • R 58 and FZ59 there can be mentioned groups chosen from aliphatic hydrocarbon radicals, aryl groups and hetero groups, or these may on the other hand be a hydrogen atom, further, some of these groups may possess substituents. Further, R 58 and FZ59 may be joined forming a nitrogen atom hetero ring nucleus.
  • the aliphatic hydrocarbon radical may be either saturated or unsaturated, and straight chain, branched chain, or cyclic. Also, it is preferably an alkyl group (e.g., methyl, ethyl, propyl, isopropyl, butyl, t-butyl, isobutyl, dodecyl, octadecyl, cyclobutyl, cyclohexyl), an alkenyl group (e.g., allyl, octenyl).
  • alkyl group e.g., methyl, ethyl, propyl, isopropyl, butyl, t-butyl, isobutyl, dodecyl, octadecyl, cyclobutyl, cyclohexyl
  • an alkenyl group e.g., allyl, octenyl
  • the aryl group is, e.g., a phenyl group or a naphthyl group, further the respective groups: a pyridinyl group, a quinolyl group, a thienyl group, a piperidyl group, an imidazolyl group are representative of the hetero radical.
  • a halogen atom and the various groups: a nitro group, a hydroxyl group, a carboxyl group, an amino group, a substituted amino group, a sulfo group, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an arylthio group, an arylazo group, an acylamino group, a carbamoyl group, a estergroup, an acyl group, an acyloxy group, a sulfonamido group, a sulfamoyl group, a sulfonyl group and a morpholino group.
  • f denotes an integer 1 to 4, m an integer 1 to 3, p an integer 1 to 5.
  • R 60 denotes an arylcarbonyl group, an alkanoyl group with 2 to 32, preferably 2 to 22, carbon atoms, an arylcarbamoyl group, an alkanecarbamoyl group with 2 to 32, preferably 2 to 22, carbon atoms, an alkoxycarbonyl group with 1 to 32, preferably 1 to 22, carbon atoms, oran aryloxycarbonyl group; these may also possess substituents, and as the substituent groups are: an alkoxy group, an alkoxycarbonyl group, an acylamino group, an alkylsulfamoyl group, an alkylsulfonamido group, an alkylsuccinimido group, a halogen atom, a nitro group, a carboxyl group, a nitrile group, an alkyl group or an aryl group.
  • R 61 denotes an arylcarbonyl group, an alkanoyl group with 2 to 32, preferably 2 to 22, carbon atoms, an aryl group, an alkanecarbamoyl group with 2 to 32, preferably 2 to 22, carbon atoms, an alkoxycarbonyl group or an aryloxycarbonyl group with 1 to 32, preferably 1 to 22, carbon atcms, an alkylsulfonyl group with 1 to 32, preferably 1 to 22, carbon atoms, an arylsulfonyl group, an aryl group, a 5-membered or 6-membered heterocyclic group (with the hetero atom chosen from a nitrogen atom, an oxygen atom, a sulfur atom, e.g., a triazolyl group, an imidazolyl group, a phthalimido group, a succinimido group, a furyl group, a pyridyl group or a benzotriazolyl group); these may
  • the yellow coupler radical in general formula (Cq-1), the case where R 51 denotes a t-butyl group or a substituted or unsubstituted aryl group, R 52 denotes a substituted or unsubstituted aryl group, and in general formula (Cq-2), the case where R 52 and R 53 denote a substituted or unsubstituted aryl group, are preferred as the yellow coupler radicals.
  • magenta coupler radical there are preferred, in general formula (Cq-3), the case in which R 54 denotes an acylamino group, a ureido group and an arylamino group, R 55 denotes a substituted aryl group, in general formula (Cq-4), the case in which R 54 denotes an acylamino group, a ureido group and an arylamino group, and R 56 denotes a hydrogen atom, and, in general formulae (Cq-5) and (Cq-6), also the case in which R 54 and R 56 denote straight chain or branched chain alkyl groups, alkenyl groups, cycloalkyl groups, aralkyl groups or cycloalkenyl groups.
  • R 57 denotes a 2-position acylamino group or ureido group, a 5-position acylamino group or alkyl group, and a 6-position hydrogen atom or chlorine atom
  • R 57 denotes a 5-position hydrogen atom, acylamino group, sulfonamido group, alkoxycarbonyl group
  • R 58 denotes a hydrogen atom
  • R 59 denotes a phenyl group, an alkyl group, an alkenyl group, a cycloalkyl group, an aralkyl group and a cycloalkenyl group.
  • R 57 denotes an acylamino group, a sulfonamido group, or a sulfamoyl group
  • R 60 and R s1 denote alkoxycarbonyl groups.
  • dimers and higher polymers may be formed; in the various moieties of these groups, there may also be polymers of monomers which have ethylenically unsaturated groups or polymers with non-color-forming monomers.
  • the coupler residual groups according to this invention denote polymers, they signify copolymers of one or more types of non-color-forming monomers which include at least one ethylene group which has no ability to couple with the oxidized form of the primary aromatic amine developer or monomers which contain a recurring unit which can be represented by general formula (Cq-13), derived from a monomer coupler which can be represented by general formula (Cq-12) given below.
  • the monomeric coupler may be two or more kinds polymerized simultaneously.
  • R denotes a hydrogen atom, a lower alkyl group with 1 to 4 carbon atoms, or a chlorine atom;
  • a 1 denotes -CONR'-, -NR'CONR'-, -NR'COO-,-COO-, -SO z -, -CO-, -NRCO-, -S0 2 NR'-, -NR'SO 2 -, -OCO-, -OCONR'-, -NR'- or -0-;
  • a 2 denotes -CONR'- or -COO-;
  • R' denotes a hydrogen atom, an aliphatic group or an aryl group; in the case where there are two or more R in one molecule, they may be the same or different.
  • A3 denotes an unsubstituted or substituted alkylene group (e.g., methylene, ethylmethylene, dimethylmethylene, dimethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, decylmethylene), an aralkylene group having 1 to 10 carbon atoms (e.g., benzylidene), or an unsubstituted or substituted arylene group (e.g., phenylene, naphthylene), the alkylene group can be straight chain or branched chain.
  • an unsubstituted or substituted alkylene group e.g., methylene, ethylmethylene, dimethylmethylene, dimethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, decylmethylene
  • an aralkylene group having 1 to 10 carbon atoms e.g., benzylidene
  • Q denotes a group which is any of the moieties R 51 to R 61 of general formulae (Cq-1) to (Cq-11) and bonded to general formula (Cq-12) or (Cq-13).
  • i, j and k denote 0 or 1, but i, j and k are not all simultaneously 0.
  • Substituent groups on the alkylene group, aralkylene group or arylene group include an aryl group (e.g., phenyl), a nitro group, a hydroxyl group, a cyano group, a sulfo group, an alkoxy group (e.g., methoxy), an aryloxy group (e.g., phenoxy), an acyloxy group (e.g., acetoxy), an acylamino group (e.g., acetylamino), a sulfonamido group (e.g., methanesulfonamido), a sulfamoyl group (e.g., methylsulfamoyl), a halogen atom (e.g., fluorine, chlorine, bromine), a carboxy group, a carbamoyl group (e.g., methylcarbamoyl), an alkoxycarbonyl group (
  • the non-color-forming ethylenic monomer which does not couple with the oxidation product of the primary aromatic amine developer there are, e.g., an acrylic acid, an a-chloroacrylic acid, an a-alkylacrylic acid, and the esters or amides derived from these acrylic acids, methylenebisacrylamide, vinyl esters, acrylonitrile, aromatic vinyl compounds, maleic acid derivatives and vinylpyridines. Two or more of the non-color-forming ethylenically unsaturated monomers can be utilized at the same time.
  • couplers can be synthesized by the methods disclosed in, for example, US-A-4,174,966, US-A-4,183,752, US-A-4,421,845, US-A-4,477,563, and JP-A-54-145135, 57-151944, 57-154234, 57-188035, 58-98728, 58-162949, 58-209736, 58-209737, 58-209738, and 58-209740.
  • the coupler represented by formula (Y) can be used in any layer such as a high-sensitive layer, a low-sensitive layer and a middle-sensitive layer or an adjacent layer thereof.
  • the amount of the coupler represented by formula (Y), which depends on its structure and use, is preferably 1 xl 0-7 to 0.5 mol, particularly preferably 1x10-s to 1 ⁇ 10 -1 mol per mol of silver in the same layeroradjacent layer.
  • the coupler represented by formula (Y) may be used singly in a layer or may be used with a known coupler.
  • the molar ratio of the coupler represented by formula (Y) and the other coupler is 0.1/99.9 to 90/10, preferably 1/99 to 50/50 (the coupler of formula (Y)/the other coupler).
  • couplers which imagewise release a nucleating agent, a development accelerator or a precursor thereof at the time of development can also be employed. Specific examples of such compounds are described, for example, in GB-B-2,097,140 and GB-B-2,131,188. Furthermore, DIR redox compound releasing couplers as described, for example, in JP-A-60-185950, couplers capable of releasing a dye which turns to a colored form after being released as described, for example, in EP-A-173,302 can also be employed in the photographic light-sensitive material of the present invention.
  • the couplers used in the present invention can be introduced into the photographic light-sensitive material according to various known dispersing methods. Specific examples of organic solvents having a high boiling point which can be employed in an oil droplet-in-water type dispersion method are described, for example, in US-A-2,322,027.
  • the color photographic light-sensitive material according to the present invention may contain, e.g., hydroquinone derivatives, aminophenol derivatives, amines, gallic acid derivatives, catechol derivatives, ascorbic acid derivatives, non-color-forming couplers and sulfonamidophenol derivatives as colorfog preventing agents or color mixing preventing agents.
  • hydroquinone derivatives aminophenol derivatives, amines, gallic acid derivatives, catechol derivatives, ascorbic acid derivatives, non-color-forming couplers and sulfonamidophenol derivatives as colorfog preventing agents or color mixing preventing agents.
  • known color fading preventing agents can be employed.
  • Typical examples of known color fading preventing agents include hindered phenols, for example, hydroquinones, 6-hydroxychromans, 5-hydroxycoumarans, spirochromans, p-alkoxyphenols and bisphenols, gallic acid derivatives, methylendixybenzenes, aminophenols, hindered amines, or ether or ester derivatives thereof derived from each of these compounds by silylation or alkylation of the phenolic hydroxy group thereof.
  • metal complexes represented by (bis-salicylaldoxymate) nickel complexes and (bis-N,N-dialkyldithiocarbamate) nickel complexes may be employed.
  • the photographic emulsion layers and other layers are coated on a flexible support such as a plastic film which is ordinarily employed for photographic light-sensitive materials.
  • various known coating methods for example, a dip coating, roller coating, a curtain coating or extrusion coating can be utilized.
  • the present invention can be applied to various color photographic light-sensitive materials.
  • Representative examples thereof include color negative films for general use or motion picture use, color reversal films for slide or television uses, color papers, color positive films and color reversal paper.
  • a color developing solution which can be used in development processing of the color photographic light-sensitive material according to the present invention is an alkaline aqueous solution preferably containing an aromatic primary amine type developing agent as a main component.
  • an aromatic primary amine type developing agent as the color developing agent, while an aminophenol type compound is useful, a p-phenylenediamine type compound is preferably employed.
  • Typical examples of the p-phenylenediamine type compounds include 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyi-N-p-hydroxyethyianiiine, 3-methyl-4-amino-N-ethyl-N- ⁇ -methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -methoxyethylaniline, or sulfate, hydrochloride, phosphate, p-toluenesulfonate, tetraphenylborate or p-(tert-octyl) benzenesulfonate thereof.
  • These diamines are preferably employed in the form of salts since the salts are generally more stable than their free forms.
  • the aminophenol type derivatives include, for example, o-aminophenol, p-aminophenol, 4-amino-2-methylphenol, 2-amino-3-methylphenol and 2-oxy-3-amino-1,4-dimethylbenzene.
  • Two or more kinds of color developing agents may be employed in a combination thereof, if desired.
  • the color developing solution can further contain pH buffering agents, such as, e.g., carbonates, borates or phosphates of alkali metals; development inhibitors or anti-fogging agents such as, e.g., bromides, iodides, benzimidazoles, benzothiazoles or mercapto compounds; preservatives such as, e.g., hydroxylamine, triethanolamine, the compounds as described in DE-A-2,622,950, sulfites or bisulfites; organic solvents such as, e.g., diethylene glycol; development accelerators such as, e.g., benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines, thiocyanates or 3,6-dithiaoctane-1,8-diol; dye forming couplers; competing couplers; nucleating agents such as, e.g., sodium borohydride; auxiliary developing agents such as,
  • aminophosphonic acids such as aminotris (methylene-phosphonic acid) and ethylenediamine-N,N,N',N'-tetramethylene-phosphonic acid, and phosphonocarboxylic acids, e.g., as described in Research Disclosure, No. 18170 (May, 1979).
  • the color developing agent typically can be used in an amount ranging generally from about 0.1 g to about 30 g, preferably from about 1 g to about 15 g, per I of the color developing solution.
  • the pH of the color developing solution used is usually 7 or more and preferably in a range from about 9 to about 13.
  • the silver halide color photographic material is imagewise exposed, subjected to color development processing as described above, and then processed with a processing solution having bleaching ability.
  • a processing solution having bleaching ability for use in the present invention practically means a processing solution which has the ability to oxidize metal silver formed upon development and colloidal silver contained in the photographic material and convert them to soluble silver salt such as silver thiocyanate complex salt or an insoluble silver salt such as a silver bromide, and includes, for example, a bleaching solution and a bleach-fixing solution. It is preferred in the present invention, that the color photographic material is processed with a processing solution having bleach-fixing ability just after color development.
  • the bleaching agents which can be used in the processing solution having bleaching ability include oxidizing agents, for example, ferric complexes such as ferricyan iron complex and ferric citrate complex, persulfates and peroxides such as hydrogen peroxide, but preferably aminopolycarboxylic acid ferric complex salts, i.e., the complex salts of ferric ions and aminopolycarboxylic acids or the salts thereof.
  • ferric complexes such as ferricyan iron complex and ferric citrate complex
  • persulfates and peroxides such as hydrogen peroxide
  • aminopolycarboxylic acid ferric complex salts i.e., the complex salts of ferric ions and aminopolycarboxylic acids or the salts thereof.
  • the aminopolycarboxylic acid ferric complex salt may be used in the form of a complex salt or may be formed in a solution using a ferric salt such as, e.g., ferric sulfate, ferric chloride, ferric nitrate, ammonium ferric sulfate and ferric phosphate, and an amino-polycarboxylic acid.
  • a ferric salt such as, e.g., ferric sulfate, ferric chloride, ferric nitrate, ammonium ferric sulfate and ferric phosphate, and an amino-polycarboxylic acid.
  • the complex salt may be used solely or as a mixture of two or more complex salts.
  • one or more types of ferric salts may be used and also one or more kinds of aminopolycarboxylic acids may be used.
  • aminopolycarboxylic acid(s) may be used in excess of the amount required for forming the ferric complex salt.
  • a combination of at least one of the above described ferric (Fe(III)) complex salts of the aminopolycarboxylic acids excluding Compound (19) and the ethylenediamine-tetraacetic acid ferric complex salt may be used.
  • a processing solution having a bleaching ability containing the above described ferric complex salt may further contain a complex salt of a metal ion other than an iron ion, such as, e.g., a cobalt ion, a nickel ion or a copper ion.
  • the amount of the bleaching agent is generally from 0.1 mol to 1 mol, preferably from 0.2 mol to 0.5 mol per I of the processing solution having bleaching ability.
  • the pH of the bleaching solution is preferably from 4.0 to 8.0, and particularly preferably from 5.0 to 7.5.
  • the processing solution having bleaching ability used in the present invention usually further contains a rehalogenating agent such as a bromide (for example, potassium bromide, sodium bromide, or ammonium bromide) and a chloride (for example, potassium chloride, sodium chloride, or ammonium chloride) in addition to the bleaching agent and the above described compound.
  • a rehalogenating agent such as a bromide (for example, potassium bromide, sodium bromide, or ammonium bromide) and a chloride (for example, potassium chloride, sodium chloride, or ammonium chloride) in addition to the bleaching agent and the above described compound.
  • the processing solution may contain known additives for conventional bleach fixing solutions, for example, at least one inorganic acid, organic acids or salts thereof having a pH buffering function, such as nitrates (for example, sodium nitrate, or ammonium nitrate), boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonte, potassium carbonate, phosphorus acid, phosphoric acid, sodium phosphate, citric acid, sodium nitrate, or tartaric acid.
  • nitrates for example, sodium nitrate, or ammonium nitrate
  • boric acid borax
  • sodium metaborate sodium metaborate
  • a fixing bath following the bleaching bath ora processing solution having a bleach-fixing ability may contain a known fixing agent(s) such as, e.g., a thiosulfate (for example, sodium thiosulfate, ammonium thiosulfate, ammonium sodium thiosulfate, or potassium thiosulfate), a thiocyanate (for example, ammonium thiocyanate, or potassium thiocyanate), thiourea and thioether.
  • the addition amount of the fixing agent is preferably about 3 mol or less, particularly preferably 2 mol or less per I of the processing solution having a fixing ability or a bleach-fixing ability.
  • the processing solution having bleach-fixing ability used in the present invention may further contain a sulfite ion releasing compound such as a sulfite (for example, sodium sulfite, or ammonium sulfite), a bisulfite, or a bisulfite addition product of an aldehyde (for example, carbonyl bisulfite).
  • a sulfite ion releasing compound such as a sulfite (for example, sodium sulfite, or ammonium sulfite), a bisulfite, or a bisulfite addition product of an aldehyde (for example, carbonyl bisulfite).
  • the processing solution having bleach-fixing ability may contain the aminopolycarboxylic acid or the salt thereof as shown above as Compounds (1) to (19), or an organic phosphonic acid compound such as, e.g., ethylenediaminetetrakismethylenephosphonic acid, diethylenetriaminepentakismethylenephosphonic acid, 1,3-diaminopropanetetrakismethylenephosphonic acid, nitro- N,N,N-trimethylenephosphonic acid or 1-hydroxyethyiidene-1,1'-diphosphonic acid.
  • an organic phosphonic acid compound such as, e.g., ethylenediaminetetrakismethylenephosphonic acid, diethylenetriaminepentakismethylenephosphonic acid, 1,3-diaminopropanetetrakismethylenephosphonic acid, nitro- N,N,N-trimethylenephosphonic acid or 1-hydroxyethyiidene-1,1'-diphosphonic acid.
  • the processing solution having bleaching ability can further contain at least one bleach accelerating agent selected from compounds having a mercapto group or a disulfide bond, isothiourea derivatives, and thiazolidine derivatives.
  • the amount of the bleach accelerating agent is preferably from 1x10- 5 to 1 x1 0-1 mol, particularly preferably from 1 x1 0-4 to 5x10- 2 mol, per I of the processing solution having bleach-fixing ability.
  • the bleach accelerating agent which can be contained in the processing solution having bleaching ability is selected from compounds having a mercapto group or a disulfide bond, thiazolidine derivatives, thiourea derivatives, and isothiourea derivatives each having a bleach accelerating effect.
  • Peferred compounds are those represented by the general formulae (a) to (g) and specific examples thereof as described in JP-A-63-163853 pages 63 to 77.
  • the bleach accelerating agent described above is generally added to the processing solution having bleaching ability, e.g., as a solution thereof in water, an alkaline aqueous solution, an organic acid or an organic solvent, but the agent may be added as a powder thereof without having any adverse influence on the bleach accelerating effect.
  • the bleach accelerating agent can be incorporated into the color photographic light-sensitive material in the present invention.
  • the bleach accelerating agent may be incorporated into any one of the blue-sensitive emulsion layer, the green-sensitive emulsion layer or the red-sensitive emulsion layer of the color photographic material or in another gelatin layer such as the uppermost layer, an intermediate layer or the lowermost layer of the color photographic material.
  • the processing bath having bleach-fixing ability may be a processing step composed of one processing tank or composed of two or more processing tanks.
  • a multistage countercurrent system may be employed with the supply of a replenisher for the processing solution or the processing solution may be successively circulated through plural tanks and the replenisher may be supplied to one of the plural tanks.
  • the silver halide color photographic material according to the present invention is generally subjected to a water washing step and/or a stabilizing step.
  • An amount of water required for the water washing step may be set in a wide range depending on, for example, characteristics of photographic light-sensitive materials (due to elements used therein, for example, couplers) uses thereof, temperature of washing water, a number of water washing tanks (stages), a replenishment system such as counter current or orderly current, or other various conditions.
  • the relationship between a number of water washing tanks and the amount of water in a multi-stage countercurrent system can be determined based on the method as described in Journal of the Society of Motion Picture and Television Engineers, Vol. 64, pages 248 to 253 (May, 1955).
  • the amount of water for washing can be significantly reduced.
  • an increase in the residence time of the water in a tank causes propagation of bacteria and some problems such as, e.g., adhesion of scum formed on the photographic materials, occur.
  • a method for reducing the amounts of calcium ions and magnesium ions as described in JP-A-62-288838 can be particularly effectively employed in order to solve such problems.
  • sterilizers for example, isothiazolone compounds as described in JP-A-57-8542, cyabendazoles, chlorine type sterilizers such as, e.g., sodium chloroisocyanurate, benzotriazoles, sterilizers as described in Hiroshi Horiguchi, Bokin Bobai No Kagaku ("Chemistry of Bactericides and Fungicides"), Biseibutsu No Mekkin-, Sakkin-, Bobai-Gijutsu ("Techniques of Sterilization, Pasteurization and Fungicides of Microorganisms"), edited by Eiseigijutsu Kai ("Sanitary technology Society”), and Bokin-Bobaizai Jiten (“Dictionary of Bactericides and Fungicides"), edited by Nippon Bokin-Bobai Gakkai (“Japan Bactericide and Fungicide Society”), can be employed.
  • chlorine type sterilizers such as, e.g., sodium chloroisocyanurate
  • the pH of the washing water used in the processing of the photographic light-sensitive materials according to the present invention is usually from 4 to 9, preferably from 5 to 8.
  • the temperature of the washing water and the time for any water washing step can be variously set depending on, e.g., characteristics or uses of the photographic light-sensitive materials. However, it is generally the case that one selects a range of from 15°C to 45°C and a period from 20 s to 10 min and preferably a range of from 25°C to 40°C and a period from 30 s to 5 min.
  • the photographic light-sensitive material of the present invention can also be directly processed with a stabilizing solution in place of the above-described water washing step.
  • a stabilizing solution any known methods as described in JP-A-57-8543, JP-A-58-14834, JP-A-59-184343, JP-A-60-220345, JP-A-60-238832, JP-A-60-239784, JP-A-60-239749, JP-A-61-4054 and JP-A-61-118749 can be employed.
  • a stabilizing bath containing 1-hydroxyethyiidene-1,1-diphosphonicacid, 5-chloro-2-methyl-4-isothiazolin-3-one, a bismuth compound and an ammonium compound is particularly preferably employed.
  • stabilizing process subsequent to the above-described water washing process is a stabilizing process subsequent to the above-described water washing process.
  • a stabilizing bath containing formalin and a surface active agent which is employed as a final bath in the processing of color photographic light-sensitive materials for photographing.
  • Emulsion A is a comparative emulsion and Emulsions B to E are high silver iodide content emulsions according to the present invention.
  • Emulsion A After desalting, 2x10- 5 mol of sodium thiosulfate and 4x10- 5 mol of chloroauric acid were added to the emulsion and the emulsion was chemically sensitized at 60°C for 60 min, whereby a silver iodobromide emulsion having an average grain size of 1.1 f..lm and containing 6 mol % of silver iodide was obtained. This emulsion was designated Emulsion A.
  • Emulsion A Using a 2% aqueous solution of gelatin containing 0.37 mol of potassium bromide and 0.10 mol of potassium iodide, the basic procedure for the preparation of Emulsion A above was repeated to obtain a silver iodobromide emulsion B having an average grain size of 1.0 ⁇ m and containing 10 mol % of silver iodide.
  • a silver iodobromide emulsion C having an average grain size of 1.0 ⁇ m and containing 12 mol % of silver iodide was obtained using a 2% aqueous solution of gelatin containing 0.35 mol of potassium bromide and 0.12 mol of potassium iodide.
  • a silver iodobromide emulsion D having an average grain size of 1.1 ⁇ m and containing 16 mol % of silver iodide was obtained using a 2% aqueous solution of gelatin containing 0.31 mol of potassium bromide and 0.16 mol of potassium iodide.
  • a silver iodobromide emulsion E having an average grain size of 1.1 ⁇ m and containing 19 mol % of silver iodide was obtained using a 2% aqueous solution of gelatin containing 0.28 mol of potassium bromide and 0.19 mol of potassium iodide.
  • Silver halide emulsion A to E thus prepared were mixed with coupler dispersions obtained by dissolving a comparative coupler and the couplers according to the present invention in an organic solvent having a high boiling point and dispersing using a homogenizer in the combinations as shown in Table 1 below, and coated on a triacetyl cellulose film support provide with a subbing layer to prepare Samples 101 to 115.
  • Coupler A
  • Samples 101 to 115 thus-obtained were exposed to white light of 20 CMS and then subjected to development processing using processing solutions after running test which was prepared in the manner as described below.
  • the samples of the present invention exhibited extremely good graininess. More specifically, the RMS value of the sample processed was measured in order to evaluate graininess. With respect to the RMS value, the description in T.H. James ed., The Theory of the Photographic Process, Fourth Edition, page 619, Macmillan Publishing Co., Inc. was followed. The samples used for measurement were prepared by processing them according to Processing Step (III) and then again subjected to desilvering to completely desilver. With respect to graininess, no substantial difference was observed between Processing Steps (I), (II) and (III).
  • Super HR-100 film manufactured by Fuji Photo Film Co., Ltd. was used to photograph standard subjects and was subjected to a running test according to Processing Steps (I), (II) or (III) shown below (500 m length). After the running test, Samples 101 to 115 were exposed to white light of 20 CMS and then subjected to development processing according to Processing Step (I) shown below.
  • stabilizing steps (1), (2) and (3) were carried out using a countercurrent stabilizing system of (3) ⁇ (2) ⁇ (1).
  • the amount of fixing solution carried over to the stabilizing tank was 2 ml per meter of the strip.
  • composition of each processing solution used is given below.
  • washing with water steps (1) and (2) were carried out using a countercurrent water washing system from Washing with Water (2) to Washing with Water (1).
  • composition of each processing solution used is given below.
  • washing with water steps (1), (2) and (3) were carried out using a three-stage countercurrent washing with water system of (3) ⁇ (2) ⁇ (1).
  • composition of each processing solution used is given below.
  • Sample 201 On a cellulose triacetate film support provided with a subbing layer was coated each layer having the composition set forth below to prepare a multilayer color photographic light-sensitive material which was designated Sample 201.
  • coated amounts of silver halide and colloidal silver are shown by g/m 2 of support of silver, the coated amounts of couplers, additives and gelatin are shown by g/m 2 of support, and the coated amounts of sensitizing dyes are shown by moles per mol of silver halide present in the same layer.
  • Twelfth Layer High-Sensitive Blue-Sensitive Emulsion Layer
  • Second Protective Layer Second Protective Layer
  • Each layer described above further contained a stabilizer for emulsion (Cpd-3: 0.04 g/m 2 ) and a surface active agent (Cpd-4: 0.02 g/m 2 ) as a coating aid in addition to the above described compounds.
  • a stabilizer for emulsion Cpd-3: 0.04 g/m 2
  • a surface active agent Cpd-4: 0.02 g/m 2
  • Samples 202 to 215 were prepared in the same manner as described for Sample 201 except that the silver halide emulsion used in the fourth layer was replaced with each of Emulsions B to E as described in Example 1, Coupler ExC-7 used in the fourth layer was substituted with the coupler according to the present invention, and Coupler ExC-2 used in the third layer was also substituted with the coupler according to the present invention as described in Table 2 below, respectively.
  • Samples 201 and 215 thus prepared were exposed to white light of 20 CMS and then subjected to development processing according to Processing Steps (I) to (III) with the processing solutions as described in Example 1 (after the running test), except that the bleaching time of Processing Step (I) was changed to 3 min, the bleach-fixing time of Processing Steps (II) was changed to 1 min, and the bleach-fixing time of Processing Step (III) was changed to 3 min, respectively.
  • the amount of remaining silver and the RMS value were determined in the same manner as described in Example 1.
  • Samples 301, 302 and 303 were prepared in the same manner as described for Sample 202 of Example 2 except ExM-8 used in the seventh layer was substituted with an-equimolar amount (calculated as a color forming unit in case of a polymer coupler) of Compound (5), (6) and (44) according to the present invention, respectively.
  • Sample 304 was prepared in the same manner as described for Sample 202 of Example 2 except ExY-15 used in the twelfth layer was substituted with an equipmolar amount of Compound (18) according to the present invention.
  • Samples 401 to 410 were prepared in the same manner as described for Samples 201 to 210 of Example 2 except ExC-2 and ExC-4 used in the third layer were substituted with an equimolar amount (which is a total mole number of ExC-2 and ExC-4) of Comparative Compound (A) and ExY-13 used in the ninth, eleventh, and twelfth layers was substituted with an equimolar amount of Comparative Compound (B), respectively.
  • Example 1 The same test as Example 1 was carried out except for removing the formalin of the Processing Steps (I) to (III). The same result as in Example 1 was obtained.
  • Example 2 The same test as Example 2 was carried out except for removing the formalin of the Processing Steps (I) to (III). The same result as in Example 2 was obtained.
  • Example 3 The same test as Example 3 was carried out except for removing the formalin of the Processing Steps (I) to (III). The same result as in Example 3 was obtained.
  • Example 4 The same test as Example 4 was carried out except for removing the formalin of the Processing Steps (I) to (III). The same result as in Example 4 was obtained.
  • silver halide color photographic materials having excellent desilvering property and good graininess can be obtained according to the present invention.

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Claims (22)

1. Matériau photographique couleur à l'halogénure d'argent comprenant un support portant au moins une couche d'émulsion d'halogénure d'argent, ledit matériau photographique couleur à l'halogénure d'argent contenant au moins une émulsion d'halogénure d'argent contenant des grains d'iodure d'argent dont la teneur moyenne en iodure est d'au moins 7 mol% et au moins un composé capable de libérer un accélérateur de blanchiment par réaction avec un produit d'oxydation d'un développateur chromogène du type amine primaire aromatique, ledit composé répondant à la formule générale (I) suivante :
Figure imgb0561
dans laquelle A représente un groupe dont la liaison avec (L1)a-(L2)b-Z peut être coupée par réaction avec un produit d'oxydation d'un agent développateur ; L1 représente un groupe retardateur ou un groupe dont la liaison avec (L2)b-Z peut être coupée par réaction avec un produit d'oxydation d'un agent développateur; L2 représente un groupe retardateur ou un groupe dont la liaison avec Z peut être coupée par réaction avec un produit d'oxydation d'un agent développateur; a et b représentent chacun 0 ou 1 et Z est un groupe représenté par l'une des formules (XII), (XIII) et (XIV) ;
Figure imgb0562
Figure imgb0563
Figure imgb0564
dans lesquelles la liaison marquée par * indique la position par laquelle le groupe est relié à A-(L1)a-(L2)b-; R31 représente un groupe aliphatique divalent en C1-C8; R32 représente un groupe défini comme pour R31, un groupe aromatique divalent en C6-C10 ou un groupe hétérocyclique divalent à 3-8 chaînons ; X1 représente -O-, -S-, -COO-, -SO2-,
Figure imgb0565
Figure imgb0566
X2 représente un groupe aromatique en C6-C10 ; X3 représente un groupe hétérocyclique à 3-8 chaînons, de préférence 5 ou 6 chaînons, contenant au moins un atome de carbone qui est relié à S dans le noyau ; Y1 représente un groupe carboxy ou un de ses sels, un groupe sulfo ou un de ses sels, un groupe hydroxy, un groupe acide phosphonique ou un de ses sels, un groupe amino qui est substitué par un groupe aliphatique en C1-C4, -NHSO2R35 ou -SO2NHR35 ; Y2 représente un groupe défini comme pour Y1 ou un atome d'hydrogène ; r représente 0 ou 1 ; f représente un entier de 0 à 4 ; m représente un entier de 1 à 4 ; u représente un entier de plus de 0 jusqu'à 4 ; pourvu que m restes Y1 puissent être reliés à une position qui peut être substituée sur R31-{(X1}r-R32}ℓ, X2-{(X1)r-R32}ℓ ou X3-{(X1)r-R32}ℓ ; lorsque m représente 2 ou plus, deux restes Y1 ou plus peuvent être les mêmes ou différents ; lorsque représente 2 ou plus, 2 restes (X1)r-R32 ou plus peuvent être les mêmes ou différents ; R33, R34 et R35 représentent chacun un atome d'hydrogène ou un groupe aliphatique en C1-C8, avec la condition que ledit composé ne soit pas
Figure imgb0567
Figure imgb0568
Figure imgb0569
2. Matériau photographique couleur à l'halogénure d'argent selon la revendication 1, dans lequel la teneur en iodure d'argent est de 10 à 30 mol%.
3. Matériau photographique couleur à l'halogénure d'argent selon la revendication 1, dans lequel le groupe représenté par A représente un groupe de coupleur ou un groupe d'oxydation-réduction.
4. Matériau photographique couleur à l'halogénure d'argent selon la revendication 3, dans lequel le groupe de coupleur représenté parAest un groupe de coupleur pour jaune, un groupe de coupleur pour magenta, un groupe de coupleur pour cyan ou un groupe de coupleur non chromogène.
5. Matériau photographique couleur à l'halogénure d'argent selon la revendication 3, dans lequel A représente un groupe de coupleur représenté par l'une des formules (Cp-1), (Cp-2), (Cp-3), (Cp-4), (Cp-5), (Cp-6), (Cp-7), (Cp-8), (Cp-9) et (Cp-1 0) ;
Figure imgb0570
Figure imgb0571
Figure imgb0572
Figure imgb0573
Figure imgb0574
Figure imgb0575
Figure imgb0576
Figure imgb0577
Figure imgb0578
dans lesquelles R41 représente un groupe aliphatique, un groupe aromatique ou un groupe hétérocyclique ; R42 représente un groupe aromatique ou un groupe hétérocyclique ; et R43, R44 et R45 représentent chacun un atome d'hydrogène, un groupe aliphatique, un groupe aromatique ou un groupe hétérocyclique ;
R51 représente un groupe défini comme pour R41 ;
R52 et R53 représentent chacun un groupe défini comme pour R42 ;
R54 représente un groupe défini comme pour R41,
Figure imgb0579
Figure imgb0580
Figure imgb0581
Figure imgb0582
ou N≡C-;
R55 représente un groupe défini comme pour R41 ;
R56 et R57 représentent chacun un groupe défini comme pour R43, R41S-, R41O-,
Figure imgb0583
R58 représente un groupe défini comme pour R41;
R59 représente un groupe défini comme pour R41,
Figure imgb0584
Figure imgb0585
, un atome d'halogène ou
Figure imgb0586
d représente un entier de 0 à 3, lorsque d représente 2 ou plus, deux restes R59 ou plus peuvent être les mêmes ou différents, ou chacun de deux restes R59 peut être un groupe divalent et relié avec l'autre pour former une structure cyclique ;
R60 représente un groupe défini comme pour R41 ;
R61 représente un groupe défini comme pour R41 ;
R62 représente un groupe défini comme pour R41, R41CONH-, R41OCONH, R41SO2NH,
Figure imgb0587
Figure imgb0588
Figure imgb0589
, un atome d'halogène ou
Figure imgb0590
R63 représente un groupe défini comme pour R41,
Figure imgb0591
Figure imgb0592
R41SO2, R41OCO-, R43OSO2-, un atome d'halogène, un groupe nitro, un groupe cyano ou R43CO- ; et
e représente un entier de 0 à 4, lorsque e représente deux ou plus, 2 restes R62 ou R63 ou plus peuvent être les mêmes ou différents.
6. Matériau photographique couleur à l'halogénure d'argent selon la revendication 3, dans lequel le groupe d'oxydation-réduction représenté par A est un groupe représenté par la formule (II) :
Figure imgb0593
dans laquelle P et Q représentent chacun un atome d'oxygène ou un groupe imino substitué ou non ; l'un au moins des n restes X et Y représente un groupe méthine substitué par un groupe (L1)a-(L2)b - Z et les autres restes X et Y représentent chacun un groupe méthine substitué ou non ou un atome d'azote ; n représente un entier de 1 à 3 (n restes X et n restes Y peuvent être les mêmes ou différents); A1 et A2 représentent chacun un atome d'hydrogène ou un groupe éliminable par un alcali; ou bien deux quelconques des substituants de P, X, Y, Q, A1 et A2 peuvent être des groupes divalents et reliés l'un avec l'autre pour former une structure cyclique.
7. Matériau photographique couleur à l'halogénure d'argent selon la revendication 6, dans lequel le groupe représenté par la formule générale (II) est un groupe représenté par la formule (III) ou la formule (IV):
Figure imgb0594
Figure imgb0595
dans lesquelles la liaison marquée d'un * indique la position par laquelle le groupe est relié à -(L1)a - (L2)b - Z ; P, Q, A1 et A2 ont chacun la même signification que dans la formule (II) ; R64 représente un substituant ; q représente 0, 1, 2 ou 3 ; et lorsque q représente 2 ou 3, deux ou trois restes R64 peuvent être les mêmes ou différents, ou bien lorsque deux restes R64 représentent des substituants situés sur les deux atomes de carbone voisins, ils peuvent être des groupes divalents reliés l'un à l'autre pour former une structure cyclique.
8. Matériau photographique couleur à l'halogénure d'argent selon la revendication 7, dans lequel P et Q représentent chacun un atome d'oxygène.
9. Matériau photographique couleur à l'halogénure d'argent selon la revendication 1, dans lequel le groupe représenté par L1 ou L2 est un groupe représenté par la formule (T-1) :
Figure imgb0596
dans laquelle la liaison marquée par * indique la position par laquelle le groupe est relié au groupe du côté gauche de la formule (I) ; la liaison marquée par ** indique la position par laquelle le groupe est relié au groupe du côté droit de la formule (I), W représente un atome d'oxygène, un atome de soufre ou un groupe
Figure imgb0597
dans lequel R67 représente un substituant ; R65 et R66 représentent chacun un atome d'hydrogène ou un substituant ; t est égal à 1 ou 2 ; lorsque t représente 2, deux groupes
Figure imgb0598
peuvent être les mêmes ou différents ; et deux quelconques des restes R65, R66 et R67 peuvent être reliés l'un à l'autre pour former une structure cyclique.
10. Matériau photographique couleur à l'halogénure d'argent selon la revendication 1, dans lequel le groupe représenté par L1 ou L2 est un groupe représenté par la formule (T-2) :
Figure imgb0599
 dans laquelle la liaison marquée par * indique la position par laquelle le groupe est relié au groupe du côté gauche dans la formule (I) ; la liaison marquée par ** indique la position par laquelle le groupe est relié au groupe du côté droit dans la formule (I) ; Nu représente un groupe nucléophile ; E représente un groupe électrophile capable de couper la liaison indiquée par ** par une attaque nucléophile de Nu ; et Link représente un groupe de liaison qui relie Nu avec E dans une position stéréochimique capable de provoquer une réaction de déplacement nucléophile intramoléculaire entre Nu et E.
11. Matériau photographique couleur à l'halogénure d'argent selon la revendication 1, dans lequel le groupe représenté par L1 ou L2 est un groupe représenté par la formule (T-3) :
Figure imgb0600
dans laquelle la liaison marquée par * indique la position par laquelle le groupe est relié au groupe du côté gauche dans la formule (I) ; la liaison marquée par ** indique la position par laquelle le groupe est relié au groupe du côté droit dans la formule (1) ; W représente un atome d'oxygène et un atome de soufre ou un groupe de formule
Figure imgb0601
dans laquelle R67 représente un substituant; R65 et R66 représentent chacun un atome d'hydrogène ou un substituant ; t représente 1 ou 2, lorsque t représente 2, deux groupes
Figure imgb0602
peuvent être identiques ou différents ; et R65 et R66 peuvent être reliés l'un à l'autre pour former une structure cyclique.
12. Matériau photographique couleur à l'halogénure d'argent selon la revendication 1, dans lequel le groupe représenté par L1 ou L2 est un groupe représenté par la formule (T-4) ou (T-5) :
Figure imgb0603
dans lesquelles la liaison marquée par * indique la position par laquelle le groupe est relié au groupe du côté gauche dans la formule (I) ; et la liaison marquée par ** indique la position par laquelle le groupe est relié au groupe du côté droit dans la formule (I).
13. Matériau photographique couleur à l'halogénure d'argent selon la revendication 1, dans lequel le groupe représenté par L1 ou L2 est un groupe représenté par la formule générale (T-6) suivante :
Figure imgb0604
dans laquelle la liaison marquée par * indique la position par laquelle le groupe est relié au groupe du côté gauche dans la formule (I) ; et la liaison marquée par ** indique la position par laquelle le groupe est relié au groupe du côté droit dans la formule (1) ; W représente un atome d'oxygène, un atome de soufre ou un groupe
Figure imgb0605
et R67 et R68 représentent chacun un substituant.
14. Matériau photographique couleur à l'halogénure d'argent selon la revendication 1, dans lequel le groupe représenté par L1 est un groupe capable de former un coupleur après avoir été séparé de A ou un groupe capable de former un groupe d'oxydation-réduction après avoir été séparé de A.
15. Matériau photographique couleur à l'halogénure d'argent selon la revendication 14, dans lequel le groupe capable de former un coupleur est un groupe représenté par la formule (V), (VI), (VII) ou (VIII) :
Figure imgb0606
Figure imgb0607
dans lesquelles la liaison marquée par * indique la position par laquelle le groupe est relié au groupe du côté gauche dans la formule (I) ; la liaison marquée par ** indique la position par laquelle le groupe est relié au groupe du côté droit dans la formule (I) ; V1 et V2 représentent chacun un substituant ; V3, V4, V5 et V6 représentent chacun un atome d'azote ou un groupe méthine substitué ou non ; V7 représente un substituant ; x représente un entier de 0 à 4 et lorsque x représente 2 ou plus, deux restes V7 ou plus peuvent être reliés l'un à l'autre pourformer une structure cyclique; V8 représente -CO-, -SO2-, un atome d'oxygène ou un groupe imino substitué ; V9 représente un groupe atomique non métallique nécessaire pour former avec
Figure imgb0608
un cycle à 5-8 chaînons; et V10 représente un atome d'hydrogène ou un substituant ; ou bien V1 et V2 peuvent représenter chacun un groupe divalent et être reliés l'un à l'autre pour former avec
Figure imgb0609
un cycle à 5-8 chaînons.
16. Matériau photographique couleur à l'halogénure d'argent selon la revendication 15, dans lequel le groupe capable de former un groupe d'oxydation-réduction est un groupe représenté par la formule (IX) : *- P'-(X' = Y')n,-Q'-A2' (IX) dans laquelle la liaison marquée par * indique la position par laquelle le groupe est relié au groupe du côté gauche dans la formule (I) ; A2', P', Q' et n'ont chacun la même signification que A2, P, Q et n dans la formule (II); l'un au moins des restes X' et Y' représente un groupe méthine substitué par un groupe -(L2)b-Z ou -Z et les autres restes X' et Y' représentent chacun un groupe méthine substitué ou non ou un atome d'azote ; ou bien deux quelconques des substituants de A1', P', Q', 'X et Y' peuvent être des groupes divalents reliés l'un à l'autre pour former une structure cyclique.
17. Matériau photographique couleur à l'halogénure d'argent selon la revendication 1, dans lequel le composé représenté par la formule (I) est un polymère dérivé d'un monomère représenté par la formule (XV) décrite ci-dessous et ayant des motifs récurrents représentés par la formule (XVI) décrite ci-dessous ou peut être un copolymère du monomère décrit ci-dessus et d'au moins un monomère non chromogène contenant au moins un groupe éthylène qui n'a pas d'aptitude au couplage avec un produit d'oxydation d'un développateur du type amine primaire aromatique :
Figure imgb0610
Figure imgb0611
dans lesquelles R représente un atome d'hydrogène, un groupe alkyle inférieur en Cl-C4 ou un atome de chlore ; A11 représente -CONH-, -NHCONH-, -NHCOO-, -COO-, -SO2-, -CO-, -NHCO-, -SO2NH-, -NHSO2-, -OCO-, -OCONH-, -NH- ou -0- ; A12 représente -CONH- ou -COO- ; A13 représente un groupe alkylène en C1-C10 substitué ou non, un groupe aralkylène substitué ou non ou un groupe arylène substitué ou non; QQ représente un groupe du composé représenté par la formule (I) ; et i, j et k représentent chacun 0 ou 1, à l'exclusion du cas où i, j et k sont simultanément 0.
18. Matériau photographique couleur à l'halogénure d'argent selon la revendication 17, dans lequel le monomère éthylénique non chromogène est choisi parmi un acide acrylique, un ester dérivé d'un acide acrylique, un amide dérivé d'un acide acrylique, un méthylènebisacrylamide, un ester vinylique, un acrylonitrile, un composé vinylique aromatique, un dérivé d'acide maléique et une vinylpyridine.
19. Matériau photographique couleur à l'halogénure d'argent selon la revendication 1, ledit matériau photographique couleur à l'halogénure d'argent contenant en outre un coupleur DIR représenté par la formule (Y):
Figure imgb0612
dans laquelle A représente un groupe de coupleur qui élimine (TIME)n-B par la réaction de couplage avec le produit d'oxydation de l'agent développateur du type amine aromatique primaire, TIME représente un groupe retardateur relié à la position active de couplage dans A et qui libère B après séparation de A par suite de la réaction de couplage, B représente un groupe représenté par les formules générales (Ila), (Ilb), (Ilc), (Ild), (Ile) (Ilf), (Ilg), (Ilh), (Ili), (Ilj), (Ilk), (IIℓ), (Ilm), (Iln), (Ilo) et (Ilp) et n représente 0 ou 1, avec la condition que lorsque n est égal à 0, B est directement relié à A :
Figure imgb0613
Figure imgb0614
Figure imgb0615
Figure imgb0616
Figure imgb0617
Figure imgb0618
Figure imgb0619
Figure imgb0620
Figure imgb0621
Figure imgb0622
Figure imgb0623
Figure imgb0624
Figure imgb0625
Figure imgb0626
Figure imgb0627
Figure imgb0628
dans lesquelles X1 représente un groupe aliphatique en C1-C4 substitué ou non ou un groupe phényle substitué ; X2 représente un atome d'hydrogène, un groupe aliphatique, un atome d'halogène, un groupe hydroxyle, un groupe alcoxy, un groupe alkylthio, un groupe alcoxycarbonyle, un groupe acylamino, un groupe carbamoyle, un groupe sulfonyle, un groupe sulfonamido, un groupe sulfamoyle, un groupe acyloxy, un groupe uréido, un groupe cyano, un groupe nitro, un groupe amino, un groupe alcoxycarbonyla- mino, un groupe aryloxycarbonyle ou un groupe acyle ; X3 représente un atome d'oxygène, un atome de soufre ou un groupe imino ayant 4 atomes de carbone ou moins ; et m représente 1 ou 2, avec la condition que le nombre m d'atomes de carbone contenu dans X2 est de 8 ou moins et lorsque m est égal à 2, deux groupes X2 peuvent être les mêmes ou différents.
20. Matériau photographique couleur à l'halogénure d'argent selon la revendication 19, dans lequel B dans la formule (Y) est représenté par la formule (Ila), (Ilb), (Ili), (Ilj), (Ilk) ou (IIℓ).
21. Matériau photographique couleur à l'halogénure d'argent selon la revendication 20, dans lequel B dans la formule (Y) est représenté par la formule (Ila), (Ili), (Ilj) ou (Ilk).
EP88116247A 1987-10-02 1988-09-30 Matériau photgraphique couleur à l'halogénure d'argent Expired - Lifetime EP0310125B1 (fr)

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JPH04212148A (ja) * 1990-05-08 1992-08-03 Fuji Photo Film Co Ltd ハロゲン化銀カラー写真感光材料及びその処理方法
JP2726777B2 (ja) * 1991-05-29 1998-03-11 富士写真フイルム株式会社 ハロゲン化銀写真感光材料
JPH05107706A (ja) * 1991-08-19 1993-04-30 Fuji Photo Film Co Ltd ハロゲン化銀カラー写真感光材料及びその処理方法
JPH0682994A (ja) * 1992-02-04 1994-03-25 Fuji Photo Film Co Ltd ハロゲン化銀カラー写真感光材料
US5464733A (en) * 1992-04-16 1995-11-07 Eastman Kodak Company Photographic material having reduced fog
US5385815A (en) 1992-07-01 1995-01-31 Eastman Kodak Company Photographic elements containing loaded ultraviolet absorbing polymer latex
JPH08202001A (ja) 1995-01-30 1996-08-09 Fuji Photo Film Co Ltd ハロゲン化銀カラー写真感光材料
US5561031A (en) * 1995-03-23 1996-10-01 Eastman Kodak Company Color reversal elements with incorporated bleach accelerator
US6221281B1 (en) 1998-11-05 2001-04-24 Nikon Corporation Liquid immersion oil
US6114103A (en) * 1998-12-30 2000-09-05 Eastman Kodak Company Photographic recording material for accelerated development
KR100846479B1 (ko) * 2006-08-21 2008-07-17 삼성에스디아이 주식회사 전기화학적 그라프팅 모노머를 포함하는 유기전해액, 및이를 채용한 리튬 전지
CN121794313A (zh) 2023-09-15 2026-04-03 富士胶片株式会社 化合物、组合物、功能性材料、卤化银照相感光材料及扩散转印型卤化银照相感光材料

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DE3853609T2 (de) 1995-08-17
EP0310125A3 (en) 1990-05-23
JPH0255A (ja) 1990-01-05
DE3853609D1 (de) 1995-05-24

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