EP0456257A1 - Farbphotographisches Silberhalogenidmaterial - Google Patents

Farbphotographisches Silberhalogenidmaterial Download PDF

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Publication number
EP0456257A1
EP0456257A1 EP91107617A EP91107617A EP0456257A1 EP 0456257 A1 EP0456257 A1 EP 0456257A1 EP 91107617 A EP91107617 A EP 91107617A EP 91107617 A EP91107617 A EP 91107617A EP 0456257 A1 EP0456257 A1 EP 0456257A1
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EP
European Patent Office
Prior art keywords
group
general formula
heterocyclic
represented
silver halide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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EP91107617A
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English (en)
French (fr)
Inventor
Keiji Mihayashi
Seiji Ichijima
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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Priority claimed from JP3036568A external-priority patent/JP2678825B2/ja
Application filed by Fuji Photo Film Co Ltd filed Critical Fuji Photo Film Co Ltd
Publication of EP0456257A1 publication Critical patent/EP0456257A1/de
Withdrawn legal-status Critical Current

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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
    • G03C7/30547—Dyes
    • 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
    • G03C7/32—Colour coupling substances
    • G03C7/3225—Combination of couplers of different kinds, e.g. yellow and magenta couplers in a same layer or in different layers of the photographic material
    • 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
    • G03C7/32—Colour coupling substances
    • G03C7/333—Coloured coupling substances, e.g. for the correction of the coloured image
    • G03C7/3335—Coloured coupling substances, e.g. for the correction of the coloured image containing an azo chromophore

Definitions

  • the present invention relates to a silver halide color photographic material. More particularly, the present invention relates to a silver halide color photographic material comprising yellow colored cyan couplers and pyrazoloazole couplers.
  • light-sensitive material One of the properties required for silver halide color photographic materials (hereinafter simply referred to as "light-sensitive material” as necessary) is color reproductivity.
  • Couplers are used in, e.g., color negative light-sensitive materials for picture taking, to correct for undesired absorption of colored dye images.
  • These colored couplers are disclosed in many publications and patents, for instance Research Disclosure No. 17643, VII-G.
  • Colored couplers used for the correction of undesired absorption of cyan images include those which exhibit a maximum absorption wavelength between about 500 nm and 600 nm in the visible light range and undergo a coupling reaction with an oxidation product of an aromatic primary amine developing agent to form a cyan dye image which exhibits a maximum absorption wavelength between about 630 nm and 750 nm.
  • a cyan dye image also has an absorption in the visible light range of 400 to 500 nm. If these undesired absorptions are also corrected for by the so-called yellow-colored cyan couplers, an effect which photographically approximates the interimage effect developed from a cyan colored image layer and a yellow colored image layer can be obtained, probably providing an advantage in color reproduction.
  • JP-A-61-221748 and JP-A-1-319774 the term "JP-A" as used herein means an "unexamined published Japanese patent application").
  • this appoach does not necessarily provide satisfactory properties, due to its low coupling reactivity and small molecular extinction coefficient.
  • This approach is also disadvantageous in that photographic properties such as the preservability of light-sensitive material and the stability of latent images are subject to great fluctuation. Thus, this approach is not yet suitable for practical use.
  • Magenta couplers for color negative light-sensitive materials for picture taking include, primarily, 5-pyrazolone couplers.
  • color negative light-sensitive materials for picture taking usually comprise yellow colored magenta couplers to correct for the undesired absorbption.
  • pyrazoloazole couplers have been rapidly developed.
  • Examples of such pyrazoloazole couplers include pyrazolotriazole couplers described in U.S. Patents 3,725,067, 4,562,146, 4,607,002, 4,675,280, 4,840,886, 4,621,046, and 4,659,652, and JP-A-61-65243, JP-A-61-65245, JP-A-61-65246, and JP-A-61-65247, pyrazolotetrazole couplers as described in JP-A-60-33552, and pyrazolopyrazole couplers as described in JP-A-60-43659.
  • couplers provide colored images having colors ranging from magenta to cyan depending on the substituents incorporated therein. These colored images exhibit no secondary absorption peak in the short wavelength range as observed in the absorption spectrum of colored images obtained from the above mentioned 5-pyrazolone couplers. These colored images have the further great advantage that they exhibit a small absorbance in the short wavelength side in the blue light range. Thus, these couplers can be said to exhibit excellent color reproductivity.
  • couplers are disadvantageous in that they do not provide a high coupling reactivity and are subject to great fluctuation in photographic properties after storage at elevated temperature and humidity after preparation of light-sensitive material or after storage at elevated temperature and humidity for a prolonged period of time between the time of picture taking and development. This makes it difficult to put this approach into practical use.
  • a silver halide color photographic material comprising a support having thereon (i) at least a silver halide emulsion layer (ii) a yellow-colored cyan coupler capable of undergoing a reaction with an oxidation product of an aromatic primary amine developing agent to release a group containing a water-soluble 6-hydroxy-2-pyridon-5-ylazo group, a water soluble 2-acylaminophenylazo group, a water soluble 2-sulfonamidophenylazo group, a water soluble 5-aminopyrazol-4-ylazo group or a water soluble pyrazolon-4-ylazo group and (iii) a coupler represented by the general formula (A): wherein R a1 represents a hydrogen atom or substituent; Xa1 represents a hydrogen atom or a group capable of being separated therefrom upon a coupling reaction with an oxidation product of an aromatic primary amine developing agent; Za, Zb and Z
  • the yellow-colored cyan coupler to be used in the present invention will be further described hereinafter.
  • the yellow colored cyan coupler of the present invention is a cyan coupler which exhibits a maximum absorption wavelength between 400 nm and 500 nm in the visible absorption range and undergoes coupling with an oxidation product of an aromatic primary amine developing agent to form a cyan dye having a maximum absorption wavelength between 630 nm and 750 nm in the visible absorption range.
  • Examples of such yellow-colored cyan couplers include couplers disclosed in JP-A-61-221748 and JP-A-1-319744.
  • a cyan coupler capable of undergoing reaction with an oxidation product of an aromatic primary amine developing agent to release a group containing a water-soluble 6-hydroxy-2-pyridon-5-ylazo group, a water-soluble pyrazolon-4-ylazo group, a water-soluble 5-aminopyrazol-4-ylazo group, a water-soluble 2-acylaminophenylazo group, or a water-soluble 2-sulfonamidophenylazo group may be preferably used in view of color reproducibility.
  • the yellow-colored cyan couplers of the present invention may be preferably represented by one of general formulae (CI) to (CIV):
  • Cp represents a cyan coupler group (T is connected to the coupling position thereof), T represents a timing group, k represents an integer 0 or 1, X represents a divalent connecting group containing N, 0 or S by which (T) k and Q are connected to each other, and Q represents an arylene group or a divalent heterocyclic group.
  • R 1 and R2 each independently represents a hydrogen atom, a carboxyl group, a sulfo group, a cyano group, an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group, a carbamoyl group, a sulfamoyl group, a carbonamido group, a sulfonamido group or an alkylsulfonyl group
  • R 3 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group, with the proviso that at least one of T, X, Q, R i , R 2 and R 3 of formula (CI) contains a water-soluble group (e.g., hydroxyl, carboxyl, sulfo, amino, ammoniumyl, phosphono, phosphino, hydroxysulfonyloxy).
  • a water-soluble group
  • R 4 represents an acyl group or sulfonyl group
  • R 5 represents a substitutable group
  • j represents an integer from 0 to 4.
  • the plurality of R 5 groups may be the same or different, with the proviso that at least one of T, X, Q, R4, and R s contains a water-soluble group (e.g., hydroxyl, carboxyl, sulfo, phosphono, phosphino, hydroxysulfonyloxy, amino, ammoniumyl).
  • R 9 represents a hydrogen atom, a carboxyl group, a sulfo group, a cyano group, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a cycloalkyloxy group, an aryloxy group, a heterocyclic group, a carbamoyl group, a sulfamoyl group, a carbonamide group, a sulfonamide group or an alkylsulfonyl group
  • R 10 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group, with the proviso that at least one of T, X, Q, R 9 , and R 10 contains a water-soluble group (e.g., hydroxyl, carboxyl, sulfo, phosphono, phosphino, hydroxysulfon
  • the groups are in tautomeric relationship with each other and thus are the same compound.
  • Examples of the coupler group represented by Cp include known cyan coupler groups (e.g., phenolic, naphtholic, diphenylimidazolic, hydroxypyridinic, long wavelength-absorbing pyrazolotriazolic cyan coupler groups).
  • known cyan coupler groups e.g., phenolic, naphtholic, diphenylimidazolic, hydroxypyridinic, long wavelength-absorbing pyrazolotriazolic cyan coupler groups.
  • Cp-6 coupler groups represented by the following general formulae (Cp-6), (Cp-7) and (Cp-8):
  • the free bond extending from the coupling position indicates the position at which a coupling-separable moiety is connected to Cp.
  • R 51 , R 52 , Rs3, R 54 or R 55 contains a nondiffusing group
  • R 51 , R 52 , R 53 , R 54 or R 55 is selected so that the total number of carbon atoms contained in R 51 , R 52 , R 53 , R 54 , or Rss is from 8 to 40, preferably 10 to 30.
  • the total number of carbon atoms contained therein is preferably 15 or less.
  • any of the above mentioned substituents represents a divalent group which connects repeating units. In this case, the total number of carbon atoms contained in these substituents may exceed the above specified ranges.
  • R 41 represents an aliphatic, aromatic or heterocyclic group
  • R 42 represents an aromatic or heterocyclic group
  • R 43 , R 44 and R 45 each represents a hydrogen atom, an aliphatic group, aromatic group or a heterocyclic group.
  • R 51 has the same meaning as R 42 .
  • Rs 2 has the same meaning as R 41 or represents R 41 CON(R 43 )-, R 41 OCON(R 43 )-, R 41 SO 2 N(R 43 )-, (R 43 )(R 44 )-NCON(R 45 )-, R 41 O-, R 41 S-, a halogen atom or (R 41 )(R 43 )N-.
  • the suffix d represents an integer from 0 to 3.
  • the suffix e represents an integer from 0 to 4.
  • the plurality of R 52 groups represent the same substituent or different substituents.
  • R 52 may be several divalent groups which are connected to each other to form a cyclic structure.
  • Typical examples of divalent groups for the formation of a cyclic structure include: wherein f represents an integer from 0 to 4; and g represents an integer from 0 to 2; when e is plural, the plurality of R 55 groups represent the same substituent or different substituents; R 53 has the same meaning as R 41 ; R 54 has the same meaning as R 41 .
  • R 55 has the same meaning as R 41 or represents R 41 OCONH-, R 41 SO 2 NH-, (R 43 )(R 44 )NCON(R 45 )-, (R 43 )(R 44 )NSO 2 N(R 45 )-, R 43 O-, R 41 S-, a halogen atom or (R 41 )(R 43 )N-group.
  • R 55 groups When there is a plurality of R 55 groups, they may be the same or different.
  • the aliphatic group is a C 1-32 , preferably C1-22 saturated or unsaturated, acyclie or cyclic, straight-chain or branched, substituted or unsubstituted aliphatic hydrocarbon group.
  • Typical examples of such an aliphatic group include methyl, ethyl, propyl, isopropyl, butyl, (t)-butyl, (i)butyl, (t)amino, hexyl, cyclohexyl, 2-ethylhexyl, octyl, 1,1,3,3-tetramethylbutyl, decyl, dodecyl, hexadecyl, and octadecyl groups.
  • the aromatic group is a C 6-20 aromatic group, and preferably is a substituted or unsubstituted phenyl group or a substituted or unsubstituted naphthyl group.
  • the heterocyclic group is a C 1-20 , preferably C 1 - 7 , preferably 3- to 8-membered substituted or unsubstituted heterocyclic group containing a hetero atom selected from nitrogen, oxygen and sulfur atoms.
  • Typical examples of such a heterocyclic group include 2-pyridyl, 2-thienyl, 2-furyl, 1,3,4-thiadiazol-2-yl, 2,4-dioxo-1,3-imidazolidin-5-yl, 1,2,4-triazol-2-yl, and 1-pyrazolyl.
  • substituents include a halogen atom, an R 47 O- group, an R 46 S-group, an R 47 CON(R 48 )- group, an (R 47 )(R 48 )NCO- group, an R 46 0CON(R 48 )- group, an R 46 SO 2 N(R 47 )-group, an (R 47 )(R 48 )NSO 2 - group, an R46S02- group, an R 47 OCO- group, an (R 47 )(R 48 )NCON(R 49 )- group, groups having the same meaning as R 46 , an R 46 COO- group, an R 47 OSO 2 - group, a cyano group, and a nitro group, wherein R 46 represents an aliphatic group, aromatic group or heterocyclic group, and R 47 , R 48 and R 49 each represents an aliphatic group, aromatic group, heterocyclic group or hydrogen
  • R 51 is preferably an aliphatic group or aromatic group.
  • R 52 is preferably a chlorine atom, aliphatic group or R 41 CONH- group.
  • the suffix d is preferably 1 or 2.
  • Rsa is preferably an aromatic group.
  • R 52 is preferably an R 41 CONH- group.
  • the suffix d is preferably 1.
  • R 54 is preferably an aliphatic group or aromatic group.
  • R 55 is preferably an R 41 OCONH- group, an R 41 CONH-group or an R 41 SO 2 NH- group. These substituents may be preferably connected to the 5- position of the naphthol ring.
  • the timing group represented by T is a group which causes cleavage of its bond to X after cleavage of its bond to Cp by a coupling reaction of a coupler with an oxidation product of an aromatic primary amine developing agent.
  • the timing group T is used for various purposes such as adjusting coupling reactivity, stabilizing couplers and adjusting the timing of release of the X containing moiety.
  • a reaction step (a) is based on a coupling reaction of quinonediimine (QDI) and a coupler, which is a well known reaction in the art.
  • QDI quinonediimine
  • a coupler which is a well known reaction in the art.
  • the timing group and the cleavage reaction thereof are known in the art.
  • timing groups (T-1) and (T-2) are disclosed in U.S. Patent 4,409,323, (T-3) is disclosed in U.S. Patent 4,421,845, (T-4) is disclosed in U.S. Patent 4,248,962,
  • T-5) is disclosed in U.S. Patent 4,652,516, (T-6) is disclosed in U.S. Patent 4,146,396
  • (T-7) is disclosed in GB Patent 1,531,927.
  • timing group T examples include the following known groups (the marks and ** indicate the position at which the timing group is connected to Cp and X, respectively):
  • R 10 represents a group capable of substituting to the benzene ring
  • R 11 has the same meaning as R 41
  • R 12 represents a hydrogen atom or substituent.
  • the suffix t represents an integer 0 to 4.
  • substituents represented by R 10 and R 12 include R 41 , a halogen atom, R 43 O-, R 43 S-, R 43 (R 44 )NCO-, R 43 OOC-, R 43 SO 2 -, R 43 (R 44 )NSO 2 -, R 43 CON(R 43 )-, R 41 SO 2 N-(R 43 )-, R 43 CO-, R 41 C 00-, R 41 SO-, nitro, R 43 (R 44 )NCON-(R 45 )-, cyano, R 41 OCON(R 43 )-, R 43 OSO 2 -.
  • R 43 (R 44 )N-, R 43 (R 44 )-NSO 2 N(R 45 ) and groups.
  • the terms R 41 , R 42
  • the suffix k represents an integer 0 or 1.
  • k is preferably 0, that is, Cp and X are preferably directly connected to each other.
  • X is a divalent connecting group which is connected to the (T) k containing moiety via a N, 0 or S atom of X.
  • a divalent connecting group include -0-, -S-, -OCO-, -OCOO-, -OCOS-, -OCONH-, -OS0 2 -, -OS0 2 NH- or a nitrogen containing heterocyclic group which is connected to the (T) k containing moiety via its nitrogen atom (e.g., groups derived from pyrrolidine, piperidine, morpholine, piperadine, pyrrole, pyrazole, imidazole, 1,2,4-triazole, benzothiazole, succinimido, phthalimido, oxazolidin-2,4-dione, imidazolidin-2,4-dione, 1,2,4-triazolidin-3,5-dione), and connecting groups obtained by combining these groups with an alkylene group
  • X is more preferably represented by the general formula (II): wherein indicates the position at which it is connected to the (T) k containing moiety; ** indicates the position at which it is connected to the Q containing moiety;
  • X 1 represents -0- or -S-;
  • L represents an alkylene group;
  • X 2 represents a single bond, -0-, -S-, -CO-, -S0 2 -, -OCO-, -COO-, -NHCO-, -CONH-, -SO 2 NH-, -NHS0 2 -, -S0 2 0-, -OS0 2 -, -OCOO-, -OCONH-, -NHCOO-, -NHCONH-, -NHSO 2 NH-, -OCOS-, -SCOO-, -OS0 2 NH- or -NHS0 2 0-; and
  • m represents an integer from 0 to 3.
  • Q represents an arylene group or divalent heterocyclic group. If Q is an arylene group, it may be a condensed ring or it may contain substituents (e.g., halogen atom, hydroxyl, carboxyl, sulfo, nitro, cyano, amino, ammonium, phosphono, phosphino, alkyl, cycloalkyl, aryl, carbonamido, sulfonamido, alkoxy, aryloxy, acyl, sulfonyl, carboxyl, carbamoyl, sulfamoyl).
  • the total number of carbon atoms contained in Q is preferably in the range of 6 to 15, more preferably, 6 to 10.
  • the heterocyclic group is a 3- to 8-membered, preferably 5-to 7-membered, single or condensed heterocyclic group containing at least one hetero atom selected from N, 0, S, P, Se and Te atoms (e.g., groups derived from pyridine, thiophene, furan, pyrrole, pyrazole, imidazole, thiazole, oxazole, benzothiazole, benzoxazole, benzofuran, benzothiophene, 1,3,4-thiadiazole, indole, quinoline).
  • the heterocyclic group may contain substituents (the same as those contained in the arylene group represented by Q).
  • the number of carbon atoms contained in Q is preferably in the range of 2 to 15, and more preferably, 2 to 10.
  • Q is most preferably a 1,4-phenylene group.
  • -(T) k -X-Q- is most preferably represented by the following formula:
  • R i , R 2 or R 3 in general formula (CI) is an alkyl group
  • the alkyl group may be either straight-chain or branched or may contain unsaturated bonds or substituents (e.g., a halogen atom, a hydroxyl, carboxyl, sulfo, phosphono, phosphino, cyano, alkoxy, aryl, alkoxycarbonyl, amino, ammoniumyl, acyl, carbonamide, sulfonamide, carbamoyl, sulfamoyl, or sulfonyl group).
  • substituents e.g., a halogen atom, a hydroxyl, carboxyl, sulfo, phosphono, phosphino, cyano, alkoxy, aryl, alkoxycarbonyl, amino, ammoniumyl, acyl, carbonamide, sulfonamide, carbamoyl, sulf
  • R 2 or R 3 is a cycloalkyl group, it is a 3- to 8-membered cycloalkyl group which may contain crosslinking groups, unsaturated bonds or substituents (the same substituents as those contained in the alkyl group represented by R i , R 2 or R 3 ).
  • R i , R 2 or R 3 is an aryl group, it may be a condensed ring or may contain substituents such as those contained in the alkyl group represented by R i , R 2 or R 3 , an alkyl and a cycloalkyl group.
  • R 1 . R 2 or R 3 is a heterocyclic group, it is a 3- to 8-membered, preferably 5- to 7-membered, single or condensed heterocyclic group containing at least one hetero atom selected from N, S, 0, P, Se and Te atoms (e.g., imidazolyl, thienyl, pyrazolyl, thiazolyl, pyridyl, quinolinyl).
  • the heterocyclic group may contain substituents (the same as those contained in the aryl group represented by R 1 , R 2 or R 3 ).
  • the carboxyl group may be a carboxylate group
  • the sulfo group may be a sulfonate group
  • the phosphino group may be a phosphinate group
  • the phosphono group may be a phosphonate group.
  • Examples of paired (counter) ions contained in these groups include Li + , Na + , K and ammonium.
  • R is preferably a hydrogen atom, a carboxyl group, a C 1-10 alkyl group (e.g., methyl, t-butyl, carbomethyl, 2-sulfomethyl, carboxymethyl, 2-carboxymethyl, 2-hydroxymethyl, benzyl, ethyl, isopropyl) or a C 6-12 aryl group (e.g., phenyl, 4-methoxyphenyl, 4-sulfophenyl). Particularly preferred among these groups are a hydrogen atom, a methyl group, and a carboxyl group.
  • a C 1-10 alkyl group e.g., methyl, t-butyl, carbomethyl, 2-sulfomethyl, carboxymethyl, 2-carboxymethyl, 2-hydroxymethyl, benzyl, ethyl, isopropyl
  • a C 6-12 aryl group e.g., phenyl, 4-methoxyphenyl, 4-sulfopheny
  • R 2 is preferably a cyano group, a carboxyl group, a C 1-10 carbamoyl group, a Co- 10 sulfamoyl group, a sulfo group, a C 1-10 alkyl group (e.g., methyl, sulfomethyl), a C 1-10 sulfonyl group (e.g., methylsulfonyl, phenylsulfonyl), a C 1-10 carbonamide group (e.g., acetamide, benzamide) or a C 1-10 sulfonamide group (e.g., methanesulfonamide, toluenesulfonamide). Particularly preferred among these groups are a cyano group, a carbamoyl group, and a carboxyl group.
  • R 3 is preferably a hydrogen atom, a C 1-12 alkyl group (e.g., methyl, sulfomethyl, carboxymethyl, 2-sulfomethyl, 2-carboxymethyl, ethyl, n-butyl, benzyl, 4-sulfobenzyl) or a C G - 15 aryl group (e.g., phenyl, 4-carboxyphenyl, 3-carboxyphenyl, 4-methoxyphenyl, 2,4-dicarboxyphenyl, 2-sulfophenyl, 3-sulfophenyl, 4-sulfophenyl, 2,4-disulfophenyl, 2,5-disulfophenyl).
  • R 3 is more preferably a C 1-7 alkyl group or a C 6-10 aryl group.
  • R 4 in general formula (CII) is an acyl group represented by the general formula (III) or a sulfonyl group represented by the general formula (IV):
  • R 1 is an alkyl, cycloalkyl, aryl or heterocyclic groups.
  • the alkyl group represented by R 11 may be either straight-chain or branched, or may contain unsaturated bonds or substituents (e.g., halogen atom, hydroxyl, carboxyl, sulfo, phosphono, phosphino, cyano, alkoxy, aryl, alkoxycarbonyl, amino, ammoniumyl, acyl, carbonamide, sulfonamide, carbamoyl, sulfamoyl, sulfonyl).
  • substituents e.g., halogen atom, hydroxyl, carboxyl, sulfo, phosphono, phosphino, cyano, alkoxy, aryl, alkoxycarbonyl, amino, ammoniumyl, acyl, carbonamide, sulfonamide, carbamoyl, sulfamoyl, sulfonyl).
  • the cycloalkyl group represented by R 1 may be a 3- to 8-membered cycloalkyl group or may contain crosslinking groups, unsaturated bonds or substituents (the same as those which can be contained in the alkyl group represented by R 11 ),
  • the aryl group represented by R 11 may be a condensed ring or may contain substituents (e.g., the same substituents as those which can be contained in the alkyl group represented by R 11 , and, in addition, an alkyl group, and a cycloalkyl group).
  • the heterocyclic group represented by R 1 is a 3- to 8-membered, preferably 5- to 7-membered single or condensed heterocyclic group containing at least one hetero atom selected from N, S, 0, P, Se and Te atoms (e.g., imidazolyl, thienyl, pyrazolyl, thiazolyl, pyridyl, quinolinyl).
  • the heterocyclic group may contain substituents (the same as those which can be contained in the aryl group represented by R 11 ),
  • the carboxyl substituent may be a carboxylate group
  • the sulfo substituent may be a sulfonate group
  • the phosphino substituent may be a phosphinate group
  • the phosphono substituent may be a phosphonate group.
  • Examples of paired (counter) ions contained in these groups include Li + , Na + , K and ammonium.
  • R 11 is preferably a C 1-10 alkyl group (e.g., methyl, carboxymethyl, sulfoethyl, cyanoethyl), a C 5-8 cycloalkyl group (e.g., cyclohexyl, 2-carboxycyclohexyl) or a C 6-10 aryl group (e.g., phenyl, 1-naphthyl, 4-sulfophenyl). Particularly preferred among these groups are a C 1 - 3 alkyl group, and a C 6 aryl group.
  • a C 1-10 alkyl group e.g., methyl, carboxymethyl, sulfoethyl, cyanoethyl
  • a C 5-8 cycloalkyl group e.g., cyclohexyl, 2-carboxycyclohexyl
  • a C 6-10 aryl group e.g., phenyl, 1-na
  • Rs is a substituent group, preferably an electron-donating group, particularly -NR 12 R 13 or -OR 14 .
  • the position at which Rs is connected to the benzene ring is preferably the 4-position.
  • R 12 , R 13 and R 14 each represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group. R 12 and R 13 may together form a ring.
  • the nitrogen-containing heterocyclic group is preferably aliphatic.
  • the suffix j represents an integer from 0 to 4, preferably 1 or 2, most preferably 1.
  • the alkyl group represented by Rg or R 10 may be either straight-chain or branched or may contain unsaturated bonds or substituents (e.g., halogen atom, hydroxyl, carboxyl, sulfo, phosphono, phosphino, cyano, alkoxy, aryl, alkoxycarbonyl, amino, ammoniumyl, acyl, carbonamide, sulfonamide, carbamoyl, sulfamoyl, sulfonyl).
  • substituents e.g., halogen atom, hydroxyl, carboxyl, sulfo, phosphono, phosphino, cyano, alkoxy, aryl, alkoxycarbonyl, amino, ammoniumyl, acyl, carbonamide, sulfonamide, carbamoyl, sulfamoyl, sulfonyl).
  • the cycloalkyl group represented by Rg or R 10 may be a 3- to 8-membered cycloalkyl group or may contain crosslinking groups, unsaturated bonds or substituents (examples of the substituents are the same as those described above as substituents for the alkyl group represented by Rg or Rio).
  • the aryl group represented by Rg or R 10 may be a condensed ring or may contain substituents (e.g., the same as those which can be contained in the alkyl group represented by R 9 or R io , and in addition alkyl, or cycloalkyl).
  • the heterocyclic group represented by Rg or R 10 is a 3- to 8-membered, preferably a 5- to 7- membered heterocyclic group, containing at least one hetero atom selected from N, S, 0, P, Se and Te atoms (imidazolyl, thienyl, pyrazolyl, thiazolyl, pyridyl, quinolinyl).
  • the heterocyclic group may contain substituents (the same as those contained in the aryl group represented by Rg or R 10 ).
  • the carboxyl substituent may be a carboxylate group
  • the sulfo substituent may be a sulfonate group
  • the phosphino substituent may be a phosphinate group
  • the phosphono substituent may be a phosphonate group.
  • Examples of paired (counter) ions in these groups include Li + , Na + , K + and ammonium.
  • Rg is preferably a cyano group, a carboxyl group, a C 1-10 carbamoyl group, a C 2-10 alkoxycarbonyl group, a C 7 - 11 aryloxycarbonyl group, a C 0-10 sulfamoyl group, sulfo group, a C 1-10 alkyl group (e.g., methyl, carboxymethyl, sulfomethyl), a C 1-10 sulfonyl group (e.g., methylsulfonyl, phenylsulfonyl), a C 1-10 carbonamido group (e.g., acetamido, benzamido), a sulfonamido group (e.g., methanesulfonamido, toluenesulfonamido), an alkyloxy group (e.g., methoxy, ethoxy) or an aryloxy group (e.g.
  • R 10 is preferably a hydrogen atom, a C 1-12 alkyl group (e.g., methyl, sulfomethyl, carboxymethyl, ethyl, 2-sulfoethyl, 2-carboxyethyl, 3-sulfopropyl, 3-carboxypropyl, 5-sulfopentyl, 5-carboxypentyl, 4-sulfobenzyl) or a C 6-15 aryl group (e.g., phenyl, 4-carboxyphenyl, 3-carboxyphenyl, 2,4-dicarboxyphenyl, 4-sulfophenyl, 3-sulfophenyl, 2,5-disulfophenyl, 2,4-disulfophenyl).
  • R 10 is more preferably a C 1-7 alkyl group or C 6-1 o aryl group.
  • Examples of the group in formula (CIV) include:
  • Examples of the group in formula (CIII) include:
  • the synthesis of the yellow-colored coupler of the present invention represented by the general formula (CI) can be normally accomplished by a diazo coupling reaction of a 6-hydroxy-2-pyridone with an aromatic diazonium salt or a heterocyclic diazonium salt having a coupler structure.
  • the synthesis of the former reaction component can be accomplished by any suitable method as disclosed in Klinsberg, (ed.) Heterocyclic Compounds--Pyridone and Its Derivatives--Part III, Interscience, (1962); Journal of the American Chemical Society, 1943, Vol. 65, page 449; Journal of the Chemical Technology & Biotechnology, 1986, Vol. 36, page 410; Tetrahedron, 1966, Vol. 22, page 445; JP-B-61-52827 (the term "JP-B” as used herein means an "examined Japanese patent publication”); West German Patents 2,162,612, 2,349,709, and 2,902,486; and U.S. Patent 3,763,170.
  • the synthesis of the latter reaction component can be accomplished by any suitable method as disclosed in U.S. Patents 4,004,929, and 4,138,258, and JP-A-61-72244 and JP-A-61-273543.
  • the diazo coupling reaction of the 6-hydroxy-2-pyridone with the diazonium salt can be effected in a solvent such as methanol, ethanol, methyl cellosolve, acetic acid, N,N-dimethylformamide, N,N-dimethylacetamide, tetrahydrofuran, dioxane, water, or a mixture thereof.
  • the base to be used in the reaction may be sodium acetate, potassium acetate, sodium carbonate, potassium carbonate, sodium hydrogencaronate, sodium hydroxide, potassium hydroxide, pyridine, triethylamine, tetramethylurea, tetramethyl guanidine or the like.
  • the reaction temperature is normally in the range of -78 °C to 60 °C, preferably -20 °C to 30 C.
  • the melting point of the compound was 269 to 272" C (decomposition).
  • the structure of the compound was confirmed by H-NMR spectrum, mass spectrum and elementary analysis.
  • the compound exhibited a maximum absorption wavelength of 457.7 nm and a molecular extinction coefficient of 41,300 in methanol.
  • the compound exhibited excellent spectral absorption characteristics as a yellow-colored coupler.
  • the compound (YC-32) is prepared by the following reaction process.
  • Compound (YC-47) is prepared by the following reaction process.
  • the synthesis of yellow-colored cyan couplers represented by the general formulae (CII) to (CIV) can be accomplished by any suitable method as described in JP-B-58-6939, JP-A-1-197563, JP-A-1-319744 and Japanese Patent Application Hei-1-316951 and those described for the method for synthesis of couplers of the general formula (CI) in the above cited patents.
  • yellow-colored cyan couplers as disclosed in the above cited JP-A-61-221748 and JP-A-1-319744 and yellow-colored cyan couplers represented by the general formulae (CI) to (CIV) can be used.
  • the couplers represented by the general formulae (CI) to (CIV) are better than those described in the above cited JP-A-61-221748 and JP-A-1-319744 in view of their coupling activity and molecular extinction coefficient.
  • the couplers of general formulae (CI) and (CII) are better than those of general formulae (CIII) and (CIV).
  • the yellow colored cyan couplers represented by the general formula (CI) are most preferable.
  • the yellow colored cyan coupler is preferably incorporated in a light-sensitive silver halide emulsion layer or in an adjacent layer thereto, particularly a red-sensitive emulsion layer, in a light-sensitive material.
  • the total amount of the yellow-colored cyan coupler to be incorporated in the light-sensitive material can be from 0.005 to 0.30 g/m 2 , preferably 0.02 to 0.20 g/m 2 , more preferably 0.03 to 0.15 g/m 2 .
  • the photographic material of the present invention contains a pyrazoloazole coupler represented by general formula (A).
  • R a1 represents a hydrogen atom or substituent
  • X a1 represents a hydrogen atom or a group capable of being separated therefrom upon a coupling reaction with an oxidation product of an aromatic primary amine developing agent
  • one of the Za-Zb and Zb-Zc bonds is a double bond and the other is a single bond
  • the Zb-Zc bond is a carbon-carbon double bond, it may be a part of an aromatic ring
  • R a ' or X a1 may form a dimer or higher polymer
  • Za, Zb or Zc is a substituted methine, it may form a dimer or higher polymer.
  • polymer means a group containing two or more groups represented by the general formulae (A) per molecule.
  • a dimer and higher polymer couplers are included in the meaning of polymer.
  • the polymer coupler may be a homopolymer comprising only a monomer unit containing a portion represented by the general formula (A) (preferably a monomer unit containing a vinyl group, hereinafter referred to as "vinyl monomer unit”) or may form a copolymer with a noncoloring ethylenically unsaturated monomer which does not undergo a coupling reaction with an oxidation product of an aromatic primary amine developing agent.
  • the compound represented by the general formula (A) is a 5-membered ring/5-membered ring condensed nitrogen-containing heterocyclic coupler.
  • the coloring nucleus of the coupler exhibits aromaticity isoelectric with naphthalene.
  • the coupler has a chemical structure commonly referred to as "azapentalene”.
  • couplers represented by the general formula (A) are 1H-imidazo[1.2-b]-pyrazoles, 1H-pyrazolo[1,5-b]pyrazole, 1H-pyrazolo[5,1-c][1,2,4]triazole, 1H-pyrazolo[1,5-b][1,2,4]triazole, 1 H-pyrazolo[1,5-d]tetrazole and 1 H-pyrazolo[1,5-a]benzimidazole represented by the general formulae (A-1 (A-2), (A-3), (A-4), (A-5) and (A-6), respectively. Preferred among these compounds are (A-1), (A-3) and (A-4). Particularly preferred among these compounds are (A-3) and (A-4).
  • the substituents R a2 , R a3 and R a4 in the general formulae (A-1) to (A-6) each represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an acyloxy group, a carbamoyloxy group, a silyloxy group, a sulfonyloxy group, an acylamino group, an anilino group, a ureido group, an imido group, a sulfamoylamino group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonamido group, a carbamoyl group, an acyl group,
  • X a1 represents a hydrogen atom, a halogen atom, a carboxyl group or a group which is connected to the carbon atom in the coupling position via an oxygen atom, a nitrogen atom or a sulfur atom to undergo coupling elimination.
  • Ra2, Ra3, Ra4 or X a1 may be a divalent group which forms a bis unit. If the portion represented by the general formula (A-1) to (A-6) is contained in a vinyl monomer unit, R a2 , R a3 or R a4 represents a bond or connecting group via which the portion represented by (A-1) to (A-6) is connected to the vinyl group.
  • R a2 , R a3 and R a4 each represents a hydrogen atom, a halogen atom (e.g., chlorine, bromine), an alkyl group (e.g., methyl, propyl, t-butyl, trifluoromethyl, tridecyl, 3-(2,4-di-t-amylphenoxy)-propyl, 2-dodecyloxyethyl, 3-phenoxypropyl, 2-hexylsulfonyl ethyl, cyclopentyl, benzyl), an aryl group (e.g., phenyl, 4-t-butylphenyl, 2,4-di-t-amylphenyl, 4-tetradecanamidophenyl, perfluorophenyl), a heterocyclic group (e.g., 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), a cyano
  • X a1 represents a hydrogen atom, a halogen atom (e.g., fluorine, chlorine, bromine, iodine), a carboxyl group, a group which is connected to the compound via an oxygen atom (e.g., acetoxy, propanoyloxy, benzoyloxy, 2,4-dichlorobenzoyloxy, ethoxyoxaloyloxy, pyruvinyloxy, cinnamoyloxy, phenoxy, 4-cyanophenoxy, 4-methanesulfonamidophenoxy, 4-methanesulfonylphenoxy, a-naphthoxy, 3-pentadecyl- phenoxy, benzyloxycarbonyloxy, ethoxy, 2-cyanoethoxy, benzyloxy, 2-phenethyloxy, 2-phenoxyethoxy, 5-phenyltetrazolyloxy, 2-benzothiazolyloxy), a group
  • R a2 , R a3 , R a4 or X a1 is a divalent group which forms a bis unit
  • a divalent group include a substituted or unsubstituted alkylene group (e.g., methylene, ethylene, 1,10-decylene, -CH 2 CH 2 -0-CH 2 CH 2 -), a substituted or unsubstituted phenylene group (e.g., 1,4-phenylene, 1,3-phenylene, and a -NHCO-R a5- CONH- group (in which R a5 represents a substituted or unsubstituted alkylene or phenylene group).
  • a substituted or unsubstituted alkylene group e.g., methylene, ethylene, 1,10-decylene, -CH 2 CH 2 -0-CH 2 CH 2 -
  • a substituted or unsubstituted phenylene group e.g., 1,
  • examples of the connecting groups represented by R a2 , R a3 or R a4 include groups formed by combining groups selected from an alkylene group (substituted or unsubstituted alkylene group, e.g., methylene, ethylene, 1,10-decylene, -CH 2 CH 2 0CH 2 CH 2 -), a phenylene group (substituted or unsubstituted phenylene group, e.g., 1,4-phenylene, 1,3-phenylene, -NHCO-, -CONH-, -0-, -OCO-, and an aralkylene group (e.g.,
  • the vinyl group contained in the vinyl monomer unit may contain substituents rather than being the group represented by the general formula (A-1) to (A-6).
  • substituents are a hydrogen atom, a chlorine atom, a C 1-4 - lower alkyl group and a substituted or unsubstituted aryl group.
  • noncoloring ethylenically unsaturated monomer unit which does not undergo a coupling reaction with an oxidation product of an aromatic primary amine developing agent examples include acrylic acid, a-chloroacrylic acid, an a-arkacrylic acid (e.g., methacrylic acid), an amido or ester derived from these acrylic acids (e.g., acrylamido, n-butylacrylamido, t-butylacrylamido, diacetonacrylamido, methacrylamido, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate, iso-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, ⁇
  • the most preferably used are the compounds represented by the general formula (A-4), particularly those of the following general formula (M): wherein R 1 represents an alkyl group, an alkoxy group or an aryloxy group; R 2 represents an acyl group or a sulfonyl group; -(L)- represents an alkylene or a phenylene group represented by -(C(R 3 )(R 4- )-CH 2 )-, with the proviso that when -(L)- is an alkylene group, the carbon atom to which R 3 and R 4- are connected is connected to the coupler nucleus, and R 3 and R 4- each represents a hydrogen atom, an alkyl group or an aryl group, but are not hydrogen atoms at the same time; and X represents an aryloxy group, an alkoxy group, a 1-azolyl group, an alkylthio group or an arylthio group.
  • R 1 , R 2 or X may be a divalent group which forms a bis unit. If the portion represented by the general formula (M) is contained in the vinyl monomer unit, any of R 1 , R 2 and X represents a bond or a connecting group via which it is connected to the vinyl group.
  • R' is an alkyl group, alkoxy group or aryloxy group.
  • R 1 is a C 1-30 straight-chain or branched alkyl group, C1-20 alkoxy group or C6-20 aryloxy group. More specifically, R 1 represents an alkyl group, such as methyl, ethyl, propyl, isopropyl, t-butyl, 2-ethylhexyl, dodecyl, 1-ethylpentyl, tridecyl, 2- methanesulfonylethyl, 3-(3-pentadecylphenoxy)propyl, 3- ⁇ 4- ⁇ 2-[4-(4-hydroxyphenylsulfonyl)phenoxy]-dodecanamide ⁇ phenyl ⁇ propyl, 2-ethoxytridecyl, trifluoromethyl, cyclohexyl, and 3-(2,4-di-t-amylphenoxy)-propyl; an alkoxy
  • These groups may contain further substituents such as a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxy group, a nitro group, a carboxy group, a sulfo group, an amino group, an alkoxy group, an aryloxy group, an acylamino group, an alkylamino group, an anilino group, a ureide group, a sulfamoylamino group, an alkylthio group, an arylthio group, an alkoxycarbonylamin6 group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, a sulfonyl group, an alkoxycarbonyl group, a heterocyclic oxy group, an azo group, an acyloxy group, a carbamoyloxy group, a silyloxy group, an aryloxy
  • R 1 is preferably an alkyl group such as methyl, ethyl, isopropyl and t-butyl, an alkoxy group such as methoxy, ethoxy, isopropoxy, 2-methoxyethoxy, and 2-phenoxyethoxy, or an aryloxy group such as phenoxy, 2-methoxyphenoxy, 4-methoxyphenoxy, and 2-methylphenoxy.
  • R 2 represents an acyl group or sulfonyl group.
  • R 2 represents an acyl group such as C 8-40 alkanoyl and aryloyl groups or sulfonyl group such as C 10-40 alkylsulfonyl and arylsulfonyl groups.
  • R 2 represents (a) a straight-chain or branched alkanoyl group such as 2-ethylhexanoyl, decanoyl, tetradecanoyl, pentadecanoyl, stearoyl and isostearoyl, straight-chain alkanoyl group represented by the general formula (A 1 ): wherein R 5 represents a hydrogen atom or alkyl group, and R 6 and R 7 each represents an alkyl group; (b) an aryloyl group such as 4-stearyloxybenzoyl, 3-(2-ethylhexanoylamino)benzoyl, 2,4-dioctyloxybenzoyl, 4-(4-dodecyloxybenzenesulfonamido)benzoyl, and 1-octyloxy-2-naphthoyl; (c) an alkylsulfonyl group such as dodecylsulfony
  • the group -(L)- represents an alkylene group represented by -C(R 3 )(R 4 )-CH 2 - wherein R 3 and R 4 each represents a hydrogen atom or an alkyl group such as methyl, ethyl, propyl, isopropyl, t-butyl and octyl or an aryl group such as phenyl, tolyl and 2-naphthyl or a phenylene group such as 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 4-methoxy-1,3-phenylene and 5-methyl-1,3-phenylene, with the proviso that R 3 and R 4 are not both hydrogen atoms at the same time.
  • -(L)- represents an alkylene group wherein R 3 and R 4 each is a hydrogen atom, a methyl group, a phenyl group or a phenylene group such as 1,3-phenylene and 1,4-phenytene.
  • X represents an aryloxy, alkoxy, 1-azolyl, alkylthio or arylthio group.
  • X represents an aryloxy group such as phenoxy, 4-methylphenoxy, 4-cyanophenoxy, 4-methanesulfonamidophenoxy, 4-acetamidophenoxy, 4-ethoxycarbonylphenoxy, 4-carboxyphenoxy, 3-carboxyphenoxy, 2-carboxyphenoxy, 4-[ ⁇ 1,1 -dimethyt-1-(4-hydroxyphenyt) ⁇ methyl]phenoxy, 4-(4-hydroxybenzenesulfonyl)phenoxy, 4-methoxyphenoxy, 1-naphthoxy, 2-phenethyloxy, 5-phenyltetrazolyloxy and 2-benzothiazolyloxy, an alkoxy group such as methoxy, ethoxy, isopropoxy, t-butoxy, ethoxycarbonylmethoxy, 2-ethoxycarbonylethoxy, 2- cyan
  • X is preferably an aryloxy group, a 1-azolyl group or an arylthio group. X is more preferably a substituted phenoxy, substituted pyrazol-1-yl or substituted phenylthio group.
  • Compounds represented by the general formula (A-1) are described in JP-A-59-162548 and U.S. Patent 4,500,630.
  • Compounds represented by the general formula (A-2) are described in JP-A-60-43659.
  • Compounds represented by the general formula (A-3) are described in JP-B-47-27411, and U.S. Patent 3,725,067.
  • Compounds represented by the general formula (A-4) are described in U.S. Patents 4,540,654, 4,705,863 and JP-A-61-65245, JP-A-62-209457 and JP-A-62-249155.
  • High coloring ballast groups as described in JP-A-58-42045, JP-A-59-214854, JP-A-59-177553, JP-A-59-177554 and JP-A-59-177557 can be appended to any of the compounds represented by the general formulae (A-1) to (A-6) and (M).
  • the system was extracted with a mixture of 150 ml of water and 150 ml of hexane.
  • the resulting aqueous phase was neutralized with 42.9 ml of concentrated hydrochloric acid and then extracted with 200 ml of ethyl acetate.
  • the resulting ethyl acetate phase was washed with a mixture of 50 ml of saturated brine and 100 ml of water twice, and then dried with sodium sulfate anhydride.
  • the ethyl acetate was distilled off by a rotary evaporator to obtain 46.1 g of Compound (2) in the form of crude product.
  • the product was immediately dispersed in 1.3 1 of methanol. 12.1 ml of pyridine was then added to the system. The system was heated to the refluxing temperature. When the tosylate was dissolved, the heating was suspended. The system was gradually cooled to room temperature with stirring. The system was stirred at room temperature for about 2 days. The methanol was then distilled off under reduced pressure so that the system was concentrated to about 300 ml. The reaction solution was then poured into about 1.5 t of water. The resulting powdered crystal was filtered off, and then dried to obtain 29.8 g (yield: 52%) of Compound (5).
  • the amine thus obtained was dissolved in 100 ml of a 1 : 1 mixture of dimethyl acetamide and acetonitrile. 4.7 ml of triethyl amine was added to the solution. A solution of 16.9 g (0.039 mol) of 2-hexyloxyethoxy-4-octylbenzenesulfonyl chloride in 40 ml of acetonitrile was added dropwise to the system with stirring under cooling with ice.
  • Compound (6) was prepared by the synthesis method as described in JP-A-64-13071 or 64-13072.
  • the conversion of Compound (6) to Compound (7) was accomplished by the synthesis example described in JP-A-62-209457.
  • the compound represented by general formula (A) may be incorporated in the red-sensitive emulsion layer and/or green-sensitive emulsion layer and/or its adjacent layers.
  • the total amount of the compound of formula (A) to be incorporated is from 0.01 to 2.00 g/m 2 , preferably 0.05 to 1.5 g/m 2 , and more preferably 0.1 to 1.0 g/m 2 .
  • the incorporation of the compounds of general formula (A) in the light-sensitive material can be effected in accordance with the method for incorporation of couplers as described later.
  • the weight proportion of the high boiling organic solvent used as a dispersing solvent for the compounds of general formula (A) is from 0 to 4.0, preferably 0 to 2.0, more preferably 0.1 to 1.5, and particularly 0.1 to 1.0.
  • the yellow-colored cyan coupler of the present invention and the coupler represented by the general formula (A) may be incorporated in the same silver halide light-sensitive layer or its adjacent layers or separately incorporated in different silver halide light-sensitive layers or adjacent light-insensitive layers.
  • the yellow-colored cyan coupler is incorporated in the red-sensitive emulsion layer and/or its adjacent light-insensitive layers
  • the coupler represented by the general formula (A) is incorporated in the green-sensitive emulsion layer and/or red-sensitive emulsion layer and/or their adjacent light-insensitive layers.
  • the yellow-colored cyan coupler is incorporated in the red-sensitive emulsion layer
  • the coupler represented by the general formula (A) is incorporated in the green-sensitive emulsion layer.
  • the silver halide color photographic material of the present invention preferably comprises at least one layer containing at least one compound represented by the general formula (I): A - ⁇ (L1) a - (B) m ⁇ P - (L2) n - DI (I) wherein A represents a group which is capable of undergoing a reaction with an oxidation product of an aromatic primary amine developing agent to cause cleavage of A from ⁇ (L1) a - (B) m ⁇ p - (L2) n - DI; L1 represents a group which causes cleavage of the bond between L1 and the group to its right as viewed in general formula (I) after cleavage of the bond between L1 and A; B represents a group which undergoes a reaction with an oxidation product of a developing agent to cause cleavage of the bond between B and the group to its right as viewed in general formula (I); L2 represents a group which causes cleavage of the bond between L2 and Di after cle
  • A represents a coupler group or a redox group.
  • Examples of the coupler group represented by A include a yellow coupler group (e.g., open-chain ketomethylene coupler group such as acylacetanilide and malondianilide), a magenta coupler group (e.g., 5-pyrazolone, pyrazolotriazole or imidazopyrazole coupler residue), a cyan coupler group (e.g., phenol coupler group, naphthol coupler group, imidazole coupler group as described in European Patent Disclosure 249,453, pyrazolopyrimidine coupler group as described in European Patent Disclosure 304,001), and a colorless coupler group (e.g., indanone coupler group, acetophenone coupler group).
  • a yellow coupler group e.g., open-chain ketomethylene coupler group such as acylacetanilide and malondianilide
  • a magenta coupler group e.g., 5-pyrazolone, pyrazolotriazole or imidazo
  • coupler group represented by A include the heterocyclic coupler groups disclosed in U.S. Patents 4,315,070, 4,183,752, 4,174,969, 3,961,959, and 4,171,223, and JP-A-52-82423.
  • the redox group represented by A is a group which undergoes cross oxidation with an oxidation product of a developing agent.
  • a redox group include hydroquinones, catechols, pyrogallols, 1,4-naphthohydroquinones, 1,2-naphthohydroquinones, sulfonamidophenols, hydrazides, and sulfonamidonaphthols. Specific examples of these groups are described in JP-A-61-230135, JP-A-62-251746, and JP-A-61-278852, U.S. Patents 3,364,022, 3,379,529, 3,639,417, and 4,684,604, and Journal of Organic Chemistry, 29, 588 (1964).
  • A is the coupler group represented by the general formulae (Cp-1 a), (Cp-2a), (Cp-3a), (Cp-4a), (Cp-5a), (Cp-6a), (Cp-7a), (Cp-8a), (Cp-9a), and (Cp-10a). These couplers exhibit an advantageously high coupling speed.
  • the mark * is indicates the position at which A is connected to - ⁇ (L1)a - (B)-m ⁇ P - (L2) n - Dl.
  • R 51a , R 52 a, R 53 a, R 54 a, R 55 a, R 56 a, R 57a , R 58a , R 59a , R 60a , R 61a , R 62 a or R 63a contains a nondiffusing group
  • these R substituents are selected such that the total number of carbon atoms contained in these R substituents is from 8 to 40, preferably 10 to 30. If these R substituents do not contain mon-diffusing groups, the total number of carbon atoms contained in these R substituents is preferably 15 or less.
  • R 51a to R 63a , l a , d a and e a will be further described hereinafter.
  • R 41a represents an aliphatic group, an aromatic group or a heterocyclic group
  • R 42a represents an aromatic group or a heterocyclic group
  • R 43a , R 44a and R 45a each represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group.
  • R 51a has the same meaning as R 43a .
  • R 52a and R 53a each has the same meaning as R 42a .
  • the suffix l a represents an integer 0 or 1.
  • R 54a has the same meaning as R 41a or represents a R41aCON(R43a)- group, a (R 41a )(R 43a )N- group, a R 41a SO 2 N(R 43a )- group, a R 41a S- group, a R 43a O- group, a (R 43a )(R 45a )NCON(R 44a )-group or a N ⁇ C- group.
  • R 55a has the same meaning as R 41a .
  • R 56a and R 57a have the same meaning as R 43a or represent a R 41a S- group, a R 43a O- group, a R 41a CON(R 43a )- group or a R 41a S0 2 N(R 43a )- group.
  • R 58a has the same meaning as R 41a .
  • R 59a has the same meaning as R 41a or represents an R 41a CON(R 43a )- group, an R 41a OCON(R 43a )- group, an R 41a SO 2 N(R 43a )- group, an (R 43a )(R 44a )NCON(R 45a )- group, an R 41a O- group, an R 41a S- group, a halogen atom, or an (R 41a )(R 43a )N- group.
  • the suffix d a represents an integer from 0 to 3.
  • the two or three R 59a groups may be the same or different substituents or they may be divalent groups which are connected to each other to form a cyclic structure.
  • R 60a has the same meaning as R 41a .
  • R 61a has the same meaning as R 41a .
  • R 62a has the same meaning as R 41a or represents a R 41a OCONH- group, a R 41a SO 2 NH- group, a (R 43a )(R 44a )NCON(R 4sa )- group, a (R 43a )(R 44a )NSO 2 N(R 45a )- group, a R 43a O- group, a R 41a S-group, a halogen atom or a (R 41a )(R 43a )N- group.
  • R 63a has the same meaning as R 41a or represents a R 43a CON(R 45a )-group, a (R 43a )(R 44a )NCO- group, a R 41a SO 2 N(R 44a )- group, a (R 43a )(R 44a )NS0 2 - group, a R 41a SO 2 - group, a R 43a OCO-group, a R 43a OSO 2 - group, a halogen atom, a nitro group, a cyano group or a R 43a CO- group.
  • the suffix e a represents an integer from 0 to 4. When there is a plurality of R 62a groups or R 63a groups, they may be the same or different.
  • the aliphatic group is a C 1-32 , preferably a C 1-22 saturated or unsaturated, acyclic or cyclic, straight-chain or branched, substituted or unsubstituted aliphatic hydrocarbon group.
  • Typical examples of such an aliphatic group include methyl, ethyl, propyl, isopropyl, butyl, (t)-butyl, (i)butyl, (t)amyl, hexyl, cyclohexyl, 2-ethylhexyl, octyl, 1,1,3,3-tetramethylbutyl, decyl, dodecyl, hexadecyl, and octadecyl groups.
  • the aromatic group is a C 6-20 aromatic group, preferably a substituted or unsubstituted phenyl group or a substituted or unsubstituted naphthyl group.
  • the heterocyclic group is a C 1-20 , preferably C 1-7 , preferably 3- to 8-membered substituted or unsubstituted heterocyclic group containing one or more nitrogen, oxygen or sulfur atoms.
  • Typical examples of such a heterocyclic group include 2-pyridyl, 2-furyl, 2-imidazolyl, 1-indolyl, 2,4-dioxo-1,3-imidazolidin-5-yl, 2-benzoxazolyl, 1,2,4-triazol-2-yl, and 1-pyrazolyl groups.
  • substituents include a halogen atom, a R 47a O- group, a R 46a S- group, a R 47a CON(R 48a )- group, a (R 47a )(R 48a )NCO- group, a R 46a OCON(R 47a )- group, a R 46a SO 2 N(R 47a )- group, a (R 47a )(R 48a )NSO 2 - group, a R 46 a S O 2 - group, a R 47 aOCO-group, a (R 47a )(R 48a )NCON(R 49a )- group, groups having the same meaning as R 46a , a R 46a COO- group, a R47aOS02- group, a cyano group, and a nitro group wherein R 46a representsan aliphatic, aromatic or heterocycl
  • R 51a to R 63a , t a , d a and e a Preferred embodiments of R 51a to R 63a , t a , d a and e a will be described hereinafter.
  • R 51a is preferably an aliphatic or aromatic group.
  • R 51a is preferably a hydrogen atom or an aliphatic group.
  • R 52a and R 55a each is preferably an aromatic group.
  • R 53a is preferably an aromatic or heterocyclic group.
  • R 54a is preferably a R 41a CONH- group or a (R 41a )(R 43a )N- group.
  • R 56a and R 57a each is preferably an aliphatic, aromatic, R 41a O-, or R 41a S- group.
  • R 58a is preferably an aliphatic or aromatic group.
  • R 59a is preferably a chlorine atom, an aliphatic or R 41a CONH-group.
  • the suffix d a is preferably 1 or 2.
  • R 60a is preferably an aromatic group.
  • R 59a is preferably a R 41a CONH- group, and d a is preferably 1.
  • R 61a is preferably an aliphatic or aromatic group.
  • e a is preferably 0 or 1.
  • R 62a is preferably a R 41a OCONH-, R 41a CONH- or R 41a SO 2 NH- group.
  • the preferred position at which these groups are connected to the coupler is the 5- position in the naphthol ring.
  • R 63a is preferably a R 41a CONH- group, a R 41a S0 2 NH- group, a (R 41a )(R 43a )NSO 2 - group, a R 41a SO 2 - group, (R 41a )(R 43a )NCO- group, a nitro group or a cyano group.
  • R 63a is preferably a (R 43a )(R 43a )NCO-, R 43a OCO- or R 43a CO- group.
  • examples of the connecting groups represented by L1 and L2 include groups subjecting a cleavage reaction of a hemiacetal described in U.S. Patents 4,146,396, 4,652,516, and 4,698,297, timing groups subjecting an intramolecular nucleophilic substitution reaction to cause a cleavage reaction as described in U.S. Patent 4,248,962, timing groups subjecting an electron migration reaction to cause a cleavage reaction as described in U.S. Patent 4,409,323 and 4,421,845, groups subjecting the hydrolyzation reaction of an iminoketal to cause a cleavage reaction as described in U.S.
  • Patent 4,546,073 and groups subjecting a hydrolyzation reaction of an ester to cause a cleavage reaction as described in West German Patent Disclosure 2,626,317.
  • L1 and L2 each is connected to A or A-(L1)a-(B)m via its hetero atom, preferably oxygen, sulfur or nitrogen atom.
  • Preferred examples of the groups represented by L1 and L2 include the following:
  • Such groups are represented by the general formula (T-1 a) below.
  • the mark * indicates the left bonding position of L1 or L2 in the compound represented by the general formula (I)
  • the mark ** indicates the right bonding position of L1 or L2 in the compound represented by the general formula (I).
  • W represents an oxygen atom, a sulfur atom or a -N(R g 7 )- group
  • R 65 and R 66 each represents a hydrogen atom or substituent
  • R 67 represents a substituent
  • t represents an integer 1 or 2.
  • the two -(W-C(R 65 )(R 66 )- groups may be the same or different.
  • Typical examples of the substituents represented by R 65 and R 66 and typical examples of R 67 include R 69 , R 69 CO-, R 69 SO 2 -, (R 69 )(R 70 )NCO-, and (R 69 )(R 70 )NSO 2 -.
  • R 69 represents an aliphatic, aromatic or heterocylic group
  • R 70 represents an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom.
  • R 65 , R 66 and R 67 may represent divalent groups which are connected to each other to form a cyclic structure. Specific examples of the group represented by the general formula (T-1 a) include the following:
  • Timing groups examples include the timing groups as described in U.S. Patent 4,248,962. These timing groups are represented by the general formula (T-2a): wherein the marks * and ** are as defined in the general formula (T-1 a); Nu represents a nucleophilic group with nucleophilic seeds such as an oxygen atom or a sulfur atom; E represents an electrophilic group which can undergo a nucleophilic attack by Nu to cause cleavage of the bond at the mark **; and Link represents a connecting group which sterically connects Nu and E so that they can undergo an intramolecular nucleophilic substitution reaction. Specific examples of the group represented by the general formula (T-2a) include the following:
  • Such groups include the connecting groups described in U.S. Patent 4,546,073. Such groups are represented by the following general formula (T-6a): wherein the marks * and ** and W are as defined in the general formula (T-1a); and R 68 has the same meaning as R 67 as defined in general formula (T-1a). Specific examples of the group represented by the general formula (T-6a) include the following:
  • the group represented by B is one which becomes a redox group or a coupler after cleavage from A-(L1) a .
  • the group represented by B is a group which has the same meaning as described above with reference to the group represented by A.
  • the group represented by B contains a group which is capable of undergoing a reaction with an oxidation product of a developing agent to eliminate the group connected to the right of B as viewed in the general formula (I).
  • Examples of the group represented by B include groups represented by B as described in JP-A-63-6550, groups represented by COUP(B) as described in U.S. Patent 4,438,193, and groups represented by RED as described in U.S. Patent 4,618,571.
  • B is preferably connected to A-(L1) a via its hetero atom, preferably oxygen atom or nitrogen atom.
  • Preferred examples of the group represented by B include those represented by the following general formulae (B-1), (B-2), (B-3), and (B-4): wherein the mark * indicates the position at which it is connected to the group to the left of B as viewed in the general formula (I); the mark ** indicates the position at which it is connected to the group to the right of B as viewed in the general formula (I); X 1 and X 4 each represents an oxygen atom or >N-SO 2 R 71 (in which R 71 represents an aliphatic, aromatic or heterocyclic group); X 2 and X 3 each represents a methine group or a nitrogen atom; and b represents an integer from 1 to 3, with the proviso that at least one of the X 2 and X 3 groups represents a methine group containing a bonding position represented by the mark ** and that when b is 2 or 3, the plurality of X 2 and X 3 groups may be the same or different.
  • X 2 and X 3 are methine groups containing substituents, they may or may not be connected to each other to form a cyclic structure (e.g., benzene ring or pyridine ring).
  • the group represented by the general formula (B-1) becomes a compound according to Kendall- Pelz' Law (T.H. James, "The Theory of the Photographic Process", 4th ed., Macmillan Publishing Co., Inc., page 299) which then undergoes reaction with an oxidation product of a developing agent to undergo oxidation.
  • R72, R 73 and R 74 each represents a group which allows the groups represented by (B-2) or (B-3) to serve as couplers containing a coupling-separatable group at the mark ** after cleavage at the mark * ; and d represents an integer from 0 to 4.
  • the R 72 groups may be the same or different.
  • the plurality of R 72 groups may be connected to each other to form a cyclic structure (e.g., benzene ring).
  • R 72 include an acyamino, alkyl, anilino, amino and alkoxy group.
  • R 73 include a phenyl group and an alkyl group.
  • R 75 , R 76 and R 77 each represents a substituent.
  • R 75 , R 76 and R 77 each represents hydrogen atom; an unsubstituted, substituted, straight chain, branched and cyclic alkyl group, for example, methyl, ethyl, i-propyl, t-butyl, octyl, allyl, cyclohexyl; an aryl group, for example, phenyl, toryl; an alkoxy group, for example, methoxy, ethoxy, ethoxyethoxy; an alkylthio group, for example, ethylthio, hexylthio; an aryloxy group, for example, phenoxy, 4-methoxyphenoxy; an arylthio group, for example, phenylthio
  • R 75 , R 76 and R 77 may be the same or different. It is preferred that R 75 and R 77 , or R 77 and R 76 combine together to form a divalent group of forming a nitrogen-containing heterocyclic group, wherein R 76 in a case of forming a ring together with R 77 and R 75 , or R 75 in a case of forming a ring together with R 77 and R 76 represents the substituent disclosed above.
  • the group represented by (B-4) becomes a coupler containing a coupling-separable group at the mark ** after cleavage at the mark * .
  • examples of the group represented by Dl include a tetrazolylthio group, a thiadiazolylthio group, an oxadiazolylthio group, a triazolylthio group, a benzimidazolyl group, a benz- thiazolylthio group, a tetrazolylseleno group, a benzoxazolylthio group, a benzotriazolyl group, a triazolyl group, and a benzoimidazolyl group. Examples of these groups are described in U.S.
  • heterocyclic groups include triazole, tetrazole, oxadiazole, thiadiazole, benzimidazole, and benzthiazole. Particularly preferred among these groups are tetrazole, 1,3,4-thiadiazole, 1,3,4-oxadiazole, and 1,2,4-triazole.
  • Z 2 is preferably a nonmetallic atom group required to form a 5- to 7-membered substituted or unsubstituted heterocyclic group (a single or condensed ring) containing a least one nitrogen atom.
  • heterocyclic groups include imidazole, 1,2,4-triazole, benzotriazole, 1,2,3-triazole, pyrazole, indazole, imidazolin-2-thione, oxazolin-2-thione, 1,2,4-triazolin-3-thione, and 1,3,4-thiadiazolin-2-thione. Particularly preferred among these groups are 1,2,3-triazole and benzotriazole.
  • Examples of the substituents to the heterocyclic group represented by the general formula (I-a) or (I-b) other than Y-COOR include an aliphatic group (C 1-6 aliphatic group, e.g., methyl, ethyl), a halogen atom (e.g., chlorine, fluorine, bromine), a heterocyclic group (C 1-5 3- to 6-membered heterocyclic group containing oxygen, sulfur or nitrogen atom as hetero atom, e.g., furyl, thienyl, imidazolyl), a nitro group, a cyano group, an aromatic group (C 6-10 aromatic group, e.g., phenyl), an amino group, an alkylthio group (C 1-10 alkylthio group, e.g., methylthio, ethylthio), and an acylamino group (C 2-8 acylamino group, e.g., acetamido, benza
  • the divalent group represented by Y is preferably an aliphatic or aromatic divalent connecting group which may contain an ether bond, a thioether bond, or a bonding group containing a hetero atom such as -NHCO-, -SO 2 -, -CO-, and -NHSOz-. Or Y may be a bond. Examples of the divalent group represented by Y include methylene, ethylene, propylene, -CH(CH 3 )-, -SCH 2 -, -SCH(CH 3 )-, -CH 2 0-CH 2 -, -SCH 2 CH 2 - and -CH 2 SCH 2 -.
  • the group represented by R is preferably a C 1-6 aliphatic group which may be substituted.
  • aliphtic groups include methyl, ethyl, propyl, butyl, isopropyl, isobutyl, isoamyl, sec-amyl, and t-amyl.
  • the R group may be substituted by various groups including an alkoxycarbonyl group (C 2 -s alkoxycarbonyl group, e.g., methoxycarbonyl, propoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, isopropoxycarbonyl, pentyloxycarbonyl, isopentyloxycarbonyl, 2-methoxyethoxycar- bonyl), a carbamoyl group (C o - s carbamoyl group, e.g., N,N-diethylcarbamoyl, N-methyl-N-ethylcarbamoyl, pyrrolidinocarbonyl, piperidinocarbonyl), a halogen atom (e.g., chlorine, fluorine), a nitro group, a cyano group, an alkoxy group (C 1-4 alkoxy group, e.g., methoxy, ethoxy, methoxyethoxy),
  • p is preferably 0 or 1.
  • the compound represented by the general formula (I) is preferably nondiffusing.
  • a nondiffusing group is preferably contained in A, L1 or B.
  • Particularly preferred among the compounds represented by the general formula (I) are those wherein A represents a coupler group.
  • the compound represented by the general formula (I) is incorporated in any of the constituent layers of the silver halide color photographic material except the support.
  • the compounds of formula (I) can be incorporated into a light-sensitive layer or a light-insensitive layer, preferably a light-sensitive layer, a layer containing silver such as colloidal silver, and their adjacent layers. More preferably, the compound (I) is incorporated in a layer containing the above mentioned yellow colored cyan coupler of the present invention or the compound represented by the general formula (A) or their adjacent layers.
  • two or more compounds represented by the general formula (1) can be incorporated in the same layer.
  • the same compound can be incorporated in two or more different layers.
  • the compound represented by the general formula (I) can be used in combination with other known DIR couplers and DIR compounds.
  • the amount of the compound (I) to be incorporated is normally from 1 x10- 2 to 50 mol%, preferably 5x10 -2 to 30 mol%, and more preferably 1 x10 -1 to 20 mol%. If incorporated in a layer free of silver, the amount is normally from 1 x10 -7 to 5x10- 4 mol/m 2 , preferably 5x10 -7 to 3x10- 4 mol/m 2 , and more preferably 1 x 10- 6 to 1 x 10- 4 mol/m 2 .
  • the incorporation of the compound represented by the general formula (I) in the light-sensitive material can be accomplished by known addition or dispersion methods as described later on.
  • the present color photographic light-sensitive material for photographing can comprise at least one blue-sensitive layer, at least one green-sensitive layer and at least one red-sensitive layer on a support.
  • the number of silver halide emulsion layers and light-insensitive layers and the order of arrangement of these layers are not specifically limited.
  • the present silver halide photographic material comprises light-sensitive layers consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity and different light sensitivities on a support.
  • the light-sensitive layers having substantially the same color sensitivity are referred to as a light-sensitive layer unit and have a color sensitivity to any of blue light, green light and red light.
  • these light-sensitive layer units are normally arranged in the order of a red-sensitive layer unit, a green-sensitive layer unit and a blue-sensitive layer unit as viewed from the support.
  • the order can be optionally reversed depending on the purpose of application.
  • two light-sensitive layers having the same color sensitivity can be arranged with a light-sensitive layer from a unit having a different color sensitivity interposed therebetween.
  • Light-insensitive layers can be provided between these silver halide light-sensitive layers and on the uppermost layer and lowermost layer.
  • interlayers can comprise couplers, DIR compounds or the like as described in JP-A-61-43748, JP-A-59-113438, JP-A-59-113440, JP-A-61-20037 and JP-A-61-20038. These interlayers can further comprise a commonly used color mixing inhibitor.
  • the plurality of silver halide emulsion layers constituting each light-sensitive layer unit can be preferably arranged in a two-layer structure, i.e., a high sensitivity emulsion layer and a low sensitivity emulsion layer, as described in West German Patent 1,121,470 and British Patent 923,045.
  • these layers are preferably arranged in an order such that the light sensitivity becomes lower towards the support.
  • a light-insensitive layer can be provided between these silver halide emulsion layers.
  • a low sensitivity emulsion layer can be provided remote from the support while a high sensitivity emulsion layer can be provided nearer the support.
  • the arrangement can be, in order, a low sensitivity blue-sensitive layer (BL), a high sensitivity blue-sensitive layer (BH), a high sensitivity green-sensitive layer (GH), a low sensitivity green-sensitive layer (GL), a high sensitivity red-sensitive layer (RH), a low sensitivity red-sensitive layer (RL)/support.
  • the order can be BH, BL, GL, GH, RH, RUsupport.
  • the order can be BH, BL, GH, GL, RL, RH/support.
  • JP-B-55-34932 a layer order of a blue-sensitive layer, GH, RH, GL, and RUsupport can be arranged.
  • a blue-sensitive layer, GL, RL, GH, RH/support can be arranged.
  • a light-sensitive layer unit may have a layer arrangement such that the uppermost layer is a silver halide emulsion layer having the highest sensitivity, the middle layer is a silver halide emulsion layer having a lower sensitivity, and the lowermost layer is a silver halide emulsion layer having a lower sensitivity than that of the middle layer.
  • the light sensitivity becomes lower towards the support.
  • the layer unit comprises three layers having different light sensitivities, a middle sensitivity emulsion layer, a high sensitivity emulsion layer and a low sensitivity emulsion layer can be arranged in this order remote from the support in a color-sensitive layer unit as described in JP-A-59-202464.
  • the order of a high sensitivity emulsion layer, a low sensitivity emulsion layer and a middle sensitivity emulsion layer or the order of a low sensitivity emulsion layer, a middle sensitivity emulsion layer and a high sensitivity emulsion layer can be used.
  • a layer unit comprises four or more layers, too, the order of arrangement of layers can be chosen and altered similarly.
  • a donor layer (CL) having an interimage effect and a different spectral sensitivity distribution from the main light-sensitive layer such as BL, GL and RL may be preferably provided adjacent or close to the main light-sensitive layer, as is disclosed in US Patents 4,663,271, 4,705,744 and 4,707,436, JP-A-62-160448 and JP-A-63-89850.
  • a suitable silver halide to be incorporated in the photographic emulsion layer in the present color light-sensitive photographic material is silver bromoiodide, silver chloroiodide or silver bromochloroiodide containing silver iodide in an amount of about 30 mol% or less. Particularly suitable is silver bromoiodide containing silver iodide in an amount of about 2 to about 10 mol%.
  • the silver halide grains in the photographic emulsions may be so-called regular grains having a regular crystal form, such as cube, octahedron and tetradecahedron, or those having an irregular crystal form such as a spherical or a tabular form, those having a crystal defect such as twinning plane, or those having a combination of these crystal forms.
  • the silver halide grains may be either fine grains having a projected area diameter of about 0.2 /.Lm or less, or large grains having a projected area diameter of up to about 10 u.m.
  • the emulsion may be either a monodisperse emulsion or a polydisperse emulsion.
  • the preparation of the silver halide photographic emulsion which can be used in the present invention can be accomplished by any suitable method described in Research Disclosure (RD) No. 17643 (December 1978), pp. 22-23, "I. Emulsion Preparation and Types", and No. 18716 (November 1979), page 648; Glafkides, Chimie et Physique Photographique, Paul Montel (1967), G.F. Duffin, Photographic Emulsion Chemistry, Focal Press, (1966); and V.L. Zelikman et al., Making and Coating Photographic Emulsion, Focal Press, (1964).
  • Tabular grains having an aspect ratio of about 3 or more can be used in the present invention.
  • the preparation of such tabular grains is easily accomplished by any suitable method such as described in Gutoff, Photograpahic Science and Engineering, Vol. 14, pp. 248-257, 1970; U.S. Patents 4,434,226, 4,414,310, 4,433,048, and 4,439,520, and British Patent 2,112,157.
  • the individual silver halide crystals may have either a homogeneous structure or a heterogeneous structure comprising a core and an outer shell differing in halogen composition, or may have a layered structure. Furthermore, the grains may have fused thereto by epitaxy a silver halide having a different halogen composition or may be bonded to a compound other than silver halide, e.g., silver thiocyanate, lead oxide, etc. Mixtures of grains having various crystal forms may also be used.
  • the above mentioned emulsion may be either the surface latent image type in which latent images are formed mainly on the surface of grains, the internal latent image type in which latent images are formed in the inside of grains, or the type in which latent images are formed both on the surface and in the inside of grains.
  • the above mentioned emulsion needs to be a negative type emulsion.
  • the above mentioned emulsion is the internal latent image type, it may be the core/shell internal latent image type emulsion described in JP-A-63-264740. The process for the preparation of such a core/shell internal latent image type emulsion is described in JP-A-59-133542.
  • the thickness of the emulsion depends on the development process and is preferably from 3 to 40 nm, particularly 5 to 20 nm.
  • the silver halide emulsion to be used in the present invention is normally subjected to physical ripening, chemical ripening and spectral sensitization. Additives to be used in these steps are described in Research Disclosure Nos. 17643, 18716, and 307105 as tabulated below.
  • two or more light-sensitive silver halide emulsions which are different in at least one characteristic, such as grain size, grain size distribution, halogen composition, grain shape and sensitivity, may be incorporated in the same layer.
  • Silver halide grains whose surface is fogged as described in U.S. Patent 4,082,553, silver halide grains whose interior is fogged as described in U.S. Patent 4,626,498 and JP-A-59-214852, and colloidal silver may be preferably incorporated in the light-sensitive silver halide emulsion layer and/or substantially light-insensitive hydrophilic colloidal layer.
  • the silver halide grains whose interior and/or surface is fogged are silver halide grains which can be uniformly (nonimagewise) developed regardless of whether they are on the exposed or unexposed portion of the light-sensitive material. The process for the preparation of silver halide grains whose interior or surface is fogged is described in U.S. Patent 4,626,498 and JP-A-59-214852.
  • Silver halides which form the core of core/shell type silver halide grains whose interior is fogged may have the same halogen composition or different halogen compositions.
  • the silver halide to be fogged on the surface or in the interior thereof may be silver chloride, silver bromochloride, silver bromoiodide and silver bromochloroiodide.
  • These fogged silver halide grains are not specifically limited in their size.
  • the average grain size is preferably from 0.01 to 0.75 IJ .m, particularly 0.05 to 0.6 am.
  • the grain shape is not specifically limited.
  • the silver halide grains may have regular crystal forms or may be polydispersant, but are preferably monodispersant (that is, at least 95% of silver halide grains by weight or grain number have grain sizes which fall within ⁇ 40% of the average grain size).
  • finely divided light-insensitive silver halide grains are preferably used.
  • Finely divided light-insensitive silver halide grains are finely divided silver halide grains which are not sensitive to light upon imagewise exposure for obtaining color images and are not substantially developed.
  • finely divided light-insensitive silver halide grains are not previously fogged.
  • the finely divided light-insensitive silver halide grains have a silver bromide content of 0 to 100 mol% and may optionally contain silver chloride and/or silver iodide, preferably 0.5 to 10 mol% silver iodide.
  • the finely divided light-insensitive silver halide grains preferably have an average grain diameter of 0.01 to 0.5 IJ .m (as calculated in terms of average of diameters of projected area corresponding to sphere), more preferably 0.02 to 0.2 um.
  • the preparation of the finely divided light-insensitive silver halide grains can be accomplished in the same manner as ordinary light-sensitive silver halide.
  • the surface of the silver halide grains does not need to be optically sensitized.
  • the silver halide grains don not need to be spectrally sensitized.
  • the silver halide emulsion preferably comprises a known stabilizer such as a triazole, azaindene, benzothiazolium or mercapto compound incorporated therein.
  • Colloidal silver may be preferably incorporated in the layer containing finely divided light-insensitive silver halide grains.
  • the amount of silver to be coated on the light-sensitive material of the present invention is preferably from 6.0 g/m 2 or less, more preferably 4.5 g/m 2 or less.
  • a compound capable of reacting with and fixing formaldehyde such as disclosed in U.S. Patents 4,411,987 and 4,435,503 can be incorporated in the light-sensitive material.
  • a compound which releases a fogging agent, a development accelerator, a silver halide solvent or precursors thereof regardless of the amount of developed silver produced by development disclosed in JP-A-1-106052 may be preferably incorporated in the light-sensitive material of the present invention.
  • a dye dispersed by the process described in International Patent Disclosure W088/04794 and JP-A-1-502912 or a dye described in EP317,308A, U.S. Patent 4,420,555, and JP-A-1-259358 may be preferably incorporated in the light-sensitive material of the present invention.
  • color couplers can be used in the present invention. Specific examples of the color couplers are described in the patents identified in the above cited Research Disclosure No. 17643, VII-C to G and No. 307105, VII-C to G.
  • the yellow couplers which are preferably used in combination with the coupler represented by the general formula (CI) to (CIV) are those described in U.S. Patents 3,933,501, 4,022,620, 4,326,024, 4,401,752, 4,248,961, 3,973,968, 4,314,023, and 4,511,649, JP-B-58-10739, British Patents 1,425,020 and 1,476,760, and European Patent 249,473A.
  • the preferred magenta couplers include 5-pyrazolone compounds and pyrazoloazole compounds. Particularly preferred are those described in U.S. Patents 4,310,619, 4,351,897, 3,061,432, 3,725,064, 4,500,630, 4,540,654, and 4,556,630, European Patent 73,636, JP-A-60-33552, JP-A-60-43659, JP-A-61-72238, JP-A-60-35730, JP-A-55-118034, and JP-A-60-185951, RD Nos. 24220 (June 1984) and 24230 (June 1984), and WO(PCT)88/04795.
  • the cyan couplers include naphthol and phenol couplers. Preferred are those described in U.S. Patents 4,052,212, 4,146,396, 4,228,233, 4,296,200, 2,369,929, 2,801,171, 2,772,162, 2,895,826, 3,772,002, 3,758,308, 4,334,011, 4,327,173, 3,446,622, 4,333,999, 4,775,616, 4,451,559, 4,427,767, 4,690,889, 4,254,212, and 4,296,199, West German Patent Disclosure No. 3,329,729, European Patents 121,365A and 249,453A, and JP-A-61-42658.
  • JP-A-64-553, JP-A-64-554, JP-A-64-555 and JP-A-64-556 and the imidazole couplers described in U.S. Patent 4,818,672 can be used.
  • Couplers which form a dye having moderate diffusibility preferably include those described in U.S. Patent 4,366,237, British Patent 2,125,570, European Patent 96,570, and West German Patent Publication No. 3,234,533.
  • colored couplers for correction of undesired absorptions of the developed color preferably include those described in Research Disclosure No. 17643, VII-G, U.S. Patents 4,163,670, 4,004,929, and 4,138,258, JP-B-57-39413, and British Patent 1,146,368.
  • couplers for correction of undesired absorptions of the developed color by a fluorescent dye released upon coupling described in U.S. Patent 4,774,181 and couplers containing as a separable group a dye precursor group capable of reacting with a developing agent to form a dye described in U.S. Patent 4,777,120 can be preferably used.
  • Couplers capable of releasing a photographically useful group upon coupling can also be used in the present invention.
  • DIR couplers which release a developing inhibitor are described in the patents cited in RD 17643, VII-F, and No. 307105, VII-F, JP-A-57-151944, JP-A-57-154234, JP-A-60-184248, and JP-A-63-37346, JP-A-63-37350 and U.S. Patents 4,248,962, and 4,782,012.
  • Bleach accelerator-releasing couplers such as described in RD Nos. 11449, and 24241, and JP-A-61-201247 are effective for reducing the time required for bleaching, particularly when incorporated in a light-sensitive material comprising the above mentioned tabular silver halide grains.
  • Couplers capable of imagewise releasing a nucleating agent or a developing accelerator at the time of development preferably include those described in British Patents 2,097,140 and 2,131,188, and JP-A-59-157638 and JP-A-59-170840.
  • Compounds which undergo a redox reaction with an oxidation product of a developing agent to release a fogging agent, development accelerator, silver halide solvent or the like such as described in JP-A-60-107029, JP-A-60-252340, JP-A-1-44940, and JP-A-1-45687 may be preferably used.
  • the photographic material according to the present invention can further comprise competing couplers such as described in U.S. Patent 4,130,427, polyequivalent couplers such as described in U.S. Patents 4,283,472, 4,338,393, and 4,310,618, DIR redox compounds or DIR couplers or DIR coupler-releasing couplers such as described in JP-A-60-185950 and JP-A-62-24252, couplers capable of releasing a dye which returns to its original color after release such as described in European Patent 173,302A, couplers capable of releasing a ligand such as described in U.S. Patent 4,553,477, couplers capable of releasing a leuco dye such as described in JP-A-63-75747, and couplers capable of releasing a fluorescent dye such as described in U.S. Patent 4,774,181.
  • competing couplers such as described in U.S. Patent 4,130,427, polyequivalent couplers such as described in U.S.
  • high boiling point solvents to be used in an oil-in-water dispersion process are described in U.S. Patent 2,322,027.
  • Specific examples of high boiling point organic solvents which have a boiling point of 175 C or higher at normal pressure and which can be used in the oil-in-water dispersion process include phthalic esters (e.g., dibutyl phthalate, dicylcohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis-(2,4-di-t-amylphenyl)phthalate, bis(2,4-di-t-amylphenyl)isophthalate, bis(1,1-diethylpropyl) phthalate), phosphoric or phosphonic esters (e.g., triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2
  • An auxiliary solvent can be used such as an organic solvent having a boiling point of about 30 C or higher, preferably 50 C to about 160° C.
  • organic solvent having a boiling point of about 30 C or higher, preferably 50 C to about 160° C.
  • Typical examples of such an organic solvent are ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, and dimethylformamide.
  • the present invention is applicable to various types of color light-sensitive materials, particularly preferably to color negative films for common use or motion picture, color reversal films for slide or television, color papers, color positive films and color reversal papers.
  • Suitable supports which can be used in the present invention are described in the above cited RD 17643 (page 28) and 18716 (right column on page 647 to left column on page 648).
  • the total thickness of all the hydrophilic colloidal layers on the emulsion side is preferably from 28 u.m or less, more preferably 23 um or less, most preferably 18 u.m or less and particularly 16 um or less.
  • the film swelling rate T ij2 is preferably 30 seconds or less, more preferably 20 seconds or less.
  • the film thickness is determined after being stored at a temperature of 25° C and a relative humidity of 55% over 2 days.
  • the film swelling rate T 1/2 can be determined by a method known in the art, e.g., by means of a swellometer of the type as described in A. Green et al, Photographic Science Engineering, Vol. 19, No. 2, pp. 124-129.
  • T 1/2 is defined as the time taken until half the saturated film thickness is reached wherein the saturated film thickness is 90% of the maximum swollen film thickness reached when the light-sensitive material is processed with a color developer at a temperature of 30 C over 195 seconds.
  • the film swelling rate T 112 can be adjusted by adding a film hardener to a gelatin binder or altering the ageing condition after coating.
  • the percentage of swelling of the light-sensitive material is preferably from 150 to 400%.
  • the percentage of swelling can be calculated from the maximum swollen film thickness determined as described above in accordance with the equation: (maximum swollen film thickness - film thickness)/film thickness.
  • one or more hydrophilic colloidal layer as backing layers having a total dried thickness of 2 to 20 u.m may be preferably provided on the side of the support opposite to the emulsion layer.
  • the backing layers preferably contain the above mentioned additives, e.g., a light absorbent, filter dye, ultraviolet absorbent, antistatic agent, film hardener, binder, plasticizer, coating aid, surface active agent, etc.
  • the percent of swelling of the backing layers is preferably from 150 to 500%.
  • the color photographic light-sensitive material according to the present invention can be developed in accordance with a conventional method as described in RD Nos 17643 (pp. 28-29) and 18716 (left column - right column on page 651).
  • the color developer to be used in the development of the present light-sensitive material is preferably an alkaline aqueous solution containing as a main component an aromatic primary amine color developing agent.
  • the color developing agent can be an aminophenolic compound.
  • p-phenylenediamine compounds are preferably used.
  • Typical examples of such p-phenylenediamine compounds include 3-methyl-4-amino-N,N-diethylaniline, 3-methy!-4-amino-N-ethyi-N- j 8-hydroxyethy!aniiine, 3-methyl-4-amino-N-ethyl-N-,6-methanesulfonamideethylaniline, 3-methyl-4-amino-N-ethyl-N-p-methox- yethylaniline, and sulfates, hydrochlorides and p-toluenesulfonates thereof. These compounds can be used in combination of two or more thereof depending on the purpose of the application.
  • the color developer normally contains a pH buffer such as carbonate and phosphate of an alkaline metal or a development inhibitor or a fog inhibitor such as bromides, iodides, benzimidazoles, ben- zothiazoles and mercapto compounds.
  • a pH buffer such as carbonate and phosphate of an alkaline metal or a development inhibitor or a fog inhibitor such as bromides, iodides, benzimidazoles, ben- zothiazoles and mercapto compounds.
  • the color developer may further contain various preservatives, e.g., hydroxylamine, diethylhydroxylamine, sulfites, hydrazines (e.g., N,N-biscarboxymethyl hydrazine), phenylsemicarbazides, triethanolamine, and catecholsulfonic acids; organic solvents, e.g., ethylene glycol and diethylene glycol; development accelerators, e.g., benzyl alcohol, polyethylene glycol, quaternary ammonium salts, and amines; color-forming couplers; competing couplers; auxiliary developing agents, e.g., 1-phenyl-3-pyrazolidone; viscosity-imparting agents; various chelating agents exemplified by aminopolycarboxylic acids, aminopolyphosphoric acids, alkylphosphonic acids, and phosphonocarboxylic acids, e.g., ethylenediaminetetraacetic acid, ni
  • Black-and-white developers to be used can contain one or more of known black-and-white developing agents, such as dihydroxybenzenes, e.g., hydroquinone, 3-pyrazolidones, e.g., 1-phenyl-3-pyrazolidone, and aminophenols, e.g., N-methyl-p-aminophenol.
  • the color developer or black-and-white developer usually has a pH of from 9 to 12.
  • the replenishment rate of the developer is usually 3 or less per m 2 of the light-sensitive material, depending on the type of the color photographic material to be processed.
  • the replenishment rate may be reduced to 500 ml/m 2 or less by decreasing the bromide ion concentration in the replenisher.
  • the replenishment rate is reduced, it is preferable to reduce the area of the liquid surface in contact with the air in the processing tank to thereby prevent evaporation and air-oxidation of the liquid.
  • the area of the liquid surface in contact with the air can be represented by the opening ratio defined as follows:
  • the opening ratio is preferably 0.1 or less, more preferably 0.001 to 0.05.
  • the reduction of the opening ratio can be accomplished by providing a cover such as a floating cover on the surface of a photographic processing solution in the processing tank, or by a process which comprises the use of a mobile cover as described in JP-A-1-82033, or a slit development process as described in JP-A-63-216050.
  • the reduction of the opening ratio can be applied not only to both the color development and black-and-white development but also to the subsequent steps such as bleach, blix, fixing, rinse and stabilization.
  • the replenishment rate can also be reduced by a means for suppressing accumulation of the bromide ion in the developing solution.
  • the color development time is normally selected between 2 and 5 minutes.
  • the color development time can be further reduced by carrying out color development at an elevated temperaure and a high pH value with a color developing solution containing a color developing agent in a high concentration.
  • the photographic emulsion layer which has been color-developed is normally subjected to bleaching and fixing to effect desilvering.
  • Bleaching may be effected simultaneously with fixing (i.e., blix), or these two steps may be carried out separately.
  • For speeding up processing bleaching may be followed by blix.
  • an embodiment wherein two blix baths connected in series are used, an embodiment wherein blix is preceded by fixing, or an embodiment wherein blix is followed by bleaching may be selected arbitrarily according to the purpose.
  • Bleaching agents to be used include compounds of polyvalent metals, e.g., iron (III), peroxides, quinones, and nitro compounds.
  • Typical examples of these bleaching agents are organic complex salts of iron (III) with aminopolycarboxylic acis, e.g., ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, and glycol ether diaminetetraacetic acid, or citric acid, tartaric acid, malic acid, etc.
  • aminopolycarboxylic acis e.g., ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, and glyco
  • aminopolycarboxylic acid-iron (III) complex salts such as (ethylenediaminetetraacetato)iron (III) complex salts are preferred for speeding up processing and for conservation of the environment.
  • aminopolycarboxylic acid-iron (III) complex salts are useful in both a bleaching solution and a blix solution.
  • the bleaching or blix solution comprising such an aminopolycarboxylic acid-iron (III) complex salt normally has a pH value of 4.0 to 8.0. For speeding up processing, it is possible to adopt a lower pH value.
  • the bleaching bath, blix bath or a prebath thereof can contain, if desired, a bleaching accelerator.
  • a bleaching accelerator examples include compounds containing a mercapto group or a disulfide group such as described in U.S. Patent 3,893,858, West German Patents 1,290,812, and 2,059,988 JP-A-53-32736, JP-A-53-57831, JP-A-53-37418, JP-A-53-72623, JP-A-95630, JP-A-53-95631, JP-A-53-104232, JP-A-53-124424, JP-A-53-141623, and JP-A-53-28426, and Research Disclosure No.
  • Preferred among these compounds are those containing a mercapto group or a disulfide group because of their great accelerating effects.
  • the compounds disclosed in U.S. Patent 3,893,858, West German Patent 1,290,812, and JP-A-53-95630 are preferred.
  • the compounds disclosed in U.S. Patent 4,552,834 are also preferred.
  • These bleaching accelerators may be incorporated into the light-sensitive material. These bleaching accelerators are particularly effective for blix of color light-sensitive materials for photographing.
  • the bleaching solution or blix solution to be used in the present invention may preferably comprise an organic acid in addition to the above mentioned compounds for the purpose of inhibiting bleach stain.
  • a particularly preferred organic acid is one having an acid dissociation constant (pKa) of 2 to 5.
  • Specific examples of such an organic acid include acetic acid, propionic acid and hydroxyacetic acid.
  • Fixing agents to be used for fixation in a fixing solution or blix solution include thiosulfates, thiocyanates, thioethers, thioureas, and a large amount of iodides.
  • the thiosulfates are normally used, with ammonium thiosulfate being applicable most often. These thiosulfates may be preferably used in combination with thiocyanates, thioether compounds, thiourea or the like.
  • As preservatives of the fixing bath or blix bath there can be preferably used sulfites, bisulfites, carbonyl bisulfite adducts or sulfinic acid compounds such as described in European Patent 294769A. Further, various aminopolycarboxylic acids or organic phosphonic acids can be added to the fixing bath or blix bath for the purpose of stabilizing the solution.
  • the total desilvering time is preferably short so long as insufficient desilvering does not result.
  • the total desilvering time is preferably from 1 to 3 minutes, more preferably 1 to 2 minutes.
  • the desilvering temperature is from 25 to 50 C, preferably 35 to 45 C. In this preferred temperature range, the desilvering rate can be improved, and the occurrence of stain after processing can be effectively inhibited.
  • agitation is preferably intensified as much as possible.
  • agitation can be intensified by various methods.
  • the processing solution may be jetted to the surface of the emulsion layer in the light-sensitive material as described in JP-A-62-183460 and JP-A-62-183461.
  • the agitating effect can be improved by a rotary means as described in JP-A-62-183461.
  • the agitating effect can be improved by moving the light-sensitive material with the emulsion surface in contact with a wiper blade provided in the bath so that turbulence occurs on the emulsion surface.
  • the agitation can be intensified by increasing the total circulated amount of processing solution.
  • Such agitation improving methods can be effectively applied to the bleaching bath, blix bath or fixing bath.
  • the improvement agitation effect expedites the supply of a bleaching agent, fixing agent or the like into the emulsion film, resulting in an improved desilvering rate.
  • the above mentioned agitation improving method is more effective when a bleach accelerator is used. In this case, the agitation improving method can remarkably enhance the bleach accelerating effect or eliminate the effect of inhibiting fixation by the bleach accelerator.
  • An automatic developing machine which can be used in the present invention is preferably equipped with a light-sensitive material conveying means as described in JP-A-60-191257, JP-A-60-191258, and JP-A-60-191259.
  • a conveying means can remarkably reduce the amount of the processing solution carried over from a bath to a succeeding bath, exhibiting a high effect of inhibiting the deterioration of properties of the processing solution.
  • Such an effect is particularly effective for the reduction of the processing time at each step or the replenishment rate of the processing solution.
  • the quantity of water to be used in the washing step can be selected from a broad range depending on the characteristics of the light-sensitive material (for example, the kind of couplers, etc.), the end use of the light-sensitive material, the temperature of washing water, the number of washing tanks (number of stages), the replenishment system (e.g., counter-flow system or direct- flow system), and other various factors. Of these factors, the relationship between the number of washing tanks and the quantity of water in the multistage counter-flow system can be obtained according to the method described in Journal of the Society of Motion Picture and Television Engineers, Vol. 64, pp. 248-253 ( May 1955).
  • isothiazolone compounds or thiabendazoles such as described in JP-A-57-8542, chlorine type bactericides, e.g., chlorinated sodium isocyanurate, benzotriazole, and bactericides described in Hiroshi Horiguchi, Bokinbobaizai no kagaku (Antibacterial and Antifungal Chemistry), Eisei Gijutsu Gakkai (ed.), Biseibutsu no mekkin, sakkin, bobigijutsu (Sterilizing and Antifungal Techniques of Microorganisms), and Nippon Bokin Bobi Gakkai (ed.), Bokin bobizai jiten (Antibacterial and Antifungal Agents Handbook) (1986).
  • the aforesaid washing step may be followed by stabilization in some cases.
  • a stabilizing bath containing a dye stabilizer and a surface active agent may be used as a final bath for color light-sensitive materials for picture taking.
  • a dye stabilizer include aldehydes such as formaldehyde and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde-sulfurous acid adducts.
  • This stabilizing bath may also contain various chelating agents or bactericides.
  • the overflow accompanying replenishment of the washing bath and/or stabilizing bath can be reused in other steps such as desilvering.
  • water may be preferably supplied to the system to make up for the concentration.
  • the silver halide color light-sensitive material may contain a color developing agent for the purpose of simplifying and expediting processing.
  • a color developing agent is preferably used in the form of various precursors.
  • precursors include indoaniline compounds as described in U.S. Patent 3,342,597, Schiff's base type compounds as described in U.S. Patent 3,342,599, and Research Disclosure Nos. 14,850 and 15,159, aldol compounds described in Research Disclosure No. 13,924, metal complexes as described in U.S. Patent 3,719,492, and urethane compounds as described in JP-A-53-135628.
  • the silver halide color light-sensitive material may optionally comprise various 1-phenyl-3-pyrazolidones for the purpose of accelerating color development. Typical examples of such compounds are described in JP-A-56-64339, JP-A-57-144547, and JP-A-58-115438.
  • the various processing solutions are used at a temperature of 10 C to 50 C.
  • the standard temperature is normally from 33°C to 38° C.
  • a higher temperature can be used to accelerate processing, thereby reducing the processing time.
  • a lower temperature can be used to improve the picture quality or the stability of the processing solutions.
  • the silver halide photographic material can also be applied to a heat-developable light-sensitive material as described in U.S. Patent 4,500,626, JP-A-60-133449, JP-A-59-218443, and JP-A-61-238056, and European Patent 210,660A2.
  • a multilayer color light-sensitive material was prepared as Specimen 101 by coating on a undercoated cellulose triacetate film support various layers having the following compositions.
  • the coated amount of silver halide and colloidal silver is represented in g/m 2 as calculated in terms of the amount of silver.
  • the coated amount of coupler, additive and gelatin is represented in g/m 2 .
  • the coated amount of sensitizing dye is represented in mol per mol of silver halide contained in the same layer.
  • the symbols indicating additives have the following meanings.
  • the additives having a plurality of effects are represented by a symbol indicating one of the effects.
  • UV ultraviolet absorbent
  • Solv high boiling organic solvent
  • ExF dye
  • ExS sensitizing dye
  • ExC cyan coupler
  • ExM magenta coupler
  • ExY yellow coupler
  • Cpd additive
  • H hardener
  • W surface active agent
  • 3rd layer Middle sensitivity red-sensitive emulsion layer
  • an emulsion stabilizer Cpd-3 (0.07 g/m 2 ), and surface active agents W-1 (0.006 g/m 2 ), W-2 (0.16 g/m 2 ), W-3 (0.10 g/m 2 ) and W-5 (0.10 g/m 2 ) were added to each of these layers as a coating aid or an emulsion dispersant.
  • Specimen 102 was prepared in the same manner as in Specimen 101, except that the present yellow-colored cyan coupler (Exemplary Compound (YC-5)) was incorporated in the 2nd, 3rd and 4th layers in the amounts of 0.04, 0.06 and 0.02 g/m 2 , respectively.
  • the present yellow-colored cyan coupler Exemplary Compound (YC-5)
  • Specimen 103 was prepared in the same manner as in Specimen 101, except that ExM-14 incorporated in the 6th, 7th and 8th layers was replaced by Exemplary Compound [A-4]-46 in equimolecular amounts.
  • Specimen 104 was prepared in the same manner as in Specimen 101, except that the yellow-colored cyan coupler used in Specimen 102 was incorporated in the 2nd, 3rd and 4th layers and Coupler [A-4]-46 of Specimen 103 was incorporated in the 6th, 7th and 8th layers.
  • Specimen 105 was prepared in the same manner as in Specimen 104, except that the yellow-colored cyan coupler (YC-5) used in the 2nd, 3rd and 4th layers of Specimen 104 was replaced by Exemplary Compound C-2 as described in JP-A-61-221748 in equimolar amounts.
  • Specimen 106 was prepared in the same manner as in Specimen 104, except that the yellow-colored cyan coupler (YC-5) used in the 2nd, 3rd and 4th layers in Specimen 104 was replaced by Exemplary Compound 11-3 as described in JP-A-1-319744 in equimolar amounts.
  • YC-5 yellow-colored cyan coupler
  • Specimens 107 an 108 were prepared in the same manner as in Specimen 104, except the yellow-colored cyan coupler (YC-5) incorporated in the 2nd, 3rd and 4th layers in Specimen 104 was replaced by Couplers (YC-1) and (YC-10) in equimolar amounts, respectively, and Coupler [A-4]-46 incorporated in the 6th, 7th and 8th layers in Specimen 104 was replaced by Couplers [A-4]-24 and [A-4]-41 in equimolar amounts, respectively.
  • YC-5 yellow-colored cyan coupler
  • Couplers (YC-1) and (YC-10) in equimolar amounts
  • Coupler [A-4]-46 incorporated in the 6th, 7th and 8th layers in Specimen 104 was replaced by Couplers [A-4]-24 and [A-4]-41 in equimolar amounts, respectively.
  • Specimens 109, 110 and 111 were prepared in the same manner as in Specimen 104, except that the yellow-colored cyan coupler (YC-5) incorporated in the 2nd, 3rd and 4th layers in Specimen 104 was replaced by Couplers (YC-37), (YC-32) and (YC-47) in equimolar amounts, respectively.
  • Specimen 112 was prepared in the same manner as in Specimen 104, except that the yellow colored cyan coupler (YC-5) incorporated in the 2nd, 3rd and 4th layers in Specimen 104 was replaced by a 1 : 1 mixture (molar ratio) of Couplers (YC-3) and (YC-16) in equimolar amounts, and the coupler [A-4]-46 incorporated in the 6th, 7th and 8th layers in Specimen 104 was replaced by a 2 : 1 mixture (molar ratio) of Couplers [A-4]-39 and [A-3]-14 in equimolar amounts.
  • the yellow colored cyan coupler (YC-5) incorporated in the 2nd, 3rd and 4th layers in Specimen 104 was replaced by a 1 : 1 mixture (molar ratio) of Couplers (YC-3) and (YC-16) in equimolar amounts
  • Specimen 113 was prepared in the same manner as in Specimen 104, except that the yellow-colored cyan coupler (YC-5) incorporated in the 2nd, 3rd and 4th layers in Specimen 104 was replaced by Couplers (YC-32), (YC-13) and (YC-5) in equimolar amounts, respectively, and the coupler [A-4]-46 incorporated in the 6th, 7th and 8th layers in Specimen 104 was replaced by Couplers [A-4]-1, [A-4]-9 and [A-4]-51 in equimolar amounts, respectively.
  • specimens were cut into 35-mm wide strips, subjected to the following tests and exposure, subjected to the following processings, and then evaluated for properties from their characteristic curves.
  • the specimens thus prepared were stored at a temperature of 25 0 C and a relative humidity of 55% for 10 days before the tests.
  • the washing step was effected in a counter-current process wherein the washing water flows backward.
  • the overflow from the washing tank (1) was all introduced into the fixing bath.
  • the overflow solution from the bleaching bath and the fixing bath were all introduced into the blix bath.
  • the amount of the developer brought over to the bleaching step, and the amount of the fixing solution brought over to the washing step were 2.5 ml and 2.0 ml per m of 35-mm wide light-sensitive material, respectively.
  • the time for crossover was 5 seconds in all the steps. This crossover time is included in the processing time of the previous step.
  • the bleaching bath, blix bath and fixing bath each had an opening ratio of 0.02.
  • the agitation in the automatic developing machine was accomplished by means of a magnet pump available from Iwaki K.K. Specifically, the processing solution was jetted through a nozzle having a diameter of 1.2 mm from the outer side of the rack to the inner side of the rack to collide with the emulsion surface of the light-sensitive material at a distance of about 10 mm.
  • the evaporation loss was made up for by the replenishment with water every day.
  • the bleaching solution was aerated only during the processing of the specimens.
  • the various processing solutions had the following compositions:
  • a 1 : 6 mixture of the above mentioned bleaching solution and fixing solution was used as the running solution.
  • the overflow solution from the above mentioned bleaching bath and fixing bath were all introduced into the blix bath.
  • washing solution (the running solution was used also as replenisher)
  • Tap water was passed through a mixed bed column packed with an H-type strongly acidic cation exchange resin (Amberlite IR-120B available from Rohm & Haas) and an OH-type strongly basic anion exchange resin (Amberlite IRA-400 available from the same company) so that the calcium and magnesium ion concentrations were each reduced to 3 mg/l or less.
  • Dichlorinated sodium isocyanurate and sodium sulfate were then added to the solution in amounts of 20 mg/t and 150 mg/t, respectively.
  • the washing solution thus obtained had a pH value of 6.5 to 7.5.
  • the processing was effected with the above mentioned processing solutions under the above mentioned conditions.
  • the same water replenisher as used for the washing solution was used.
  • Table 2 above shows that the use of the yellow-colored cyan couplers of the present invention provides improved inhibition of color stain in cyan images. It is also shown that the yellow-colored cyan couplers of the present invention provide better results than do the comparative couplers. It is further shown that the use of the yellow-colored cyan couplers provides a high sensitivity and remarkable improvements in the preservability of the light-sensitive material and the stability of latent images as compared to the use of the comparative yellow-colored cyan couplers.
  • couplers represented by the general formula (A) provides a high sensitivity and improvements in preservability of light-sensitive material and stability of latent images.
  • the combination of the yellow-colored cyan coupler of the present invention and the coupler represented by the general formula (A) provides better improvements in preservability of light-sensitive material and stability of latent images over the separate use of these couplers.
  • the couplers which release 6-hydroxy-2-pyridon-5-ylazo group are best in the the properties tested in the present example.
  • the couplers which release 2-acylaminophenylazo group and 2-sulfonamidephenylazo group are ranked next.
  • the couplers which release pyrazolon-4-ylazo group are ranked next.
  • a multilayer color light-sensitive material Specimen 201 was prepared by coating on an undercoated cellulose triacetate film support the following layers.
  • the figures indicate the coated amount of each component in g/m 2.
  • the coated amount of silver halide and colloidal silver are represented in terms of the amount of silver.
  • the coated amount of sensitizing dye is represented in mol amount per mol of silver halide contained in the same layer.
  • 3rd layer Low sensitivity red-sensitive emulsion layer
  • llth layer High sensitivity blue-sensitive emulsion layer
  • a coating aid W-2 In addition to these compounds, a coating aid W-2, a dispersion aid W-3, film hardeners H-1 and H-2, an antiseptic agent Cpd-4, a stabilizer Cpd-5, and fog inhibitors Cpd-6 and Cpd-7 were added to each of these layers.
  • Specimen 202 was prepared in the same manner as Specimen 201, except that the yellow-colored cyan coupler (YC-18) was coated on the 3rd and 4th layers in an amount of 0.02 g/m 2 , ExM-1 incorporated in the 6th layer was replaced by [A-3]-11 in an equimolar amount, and ExM-2 incorporated in the 8th layer was replaced by [A-3]-14 in an equimolar amount.
  • YC-18 yellow-colored cyan coupler
  • Specimens 203 to 209 were prepared in the same manner as Specimen 202, except that the yellow-colored cyan couplers as set forth in Table 3 were incorporated in the 3rd and 4th layers and the couplers incorporated in the 6th layer and 8th layer were replaced by the couplers represented by the general formula (A) in equimolar amounts, respectively.
  • Specimen 210 was prepared in the same manner as Specimen 202 except that the amount of ExC-1 incorporated in the 3rd layer was reduced to 0.80 g/m 2 and the loss was made up for by an equimolar amount of [A-3]-17. Additionally, the yellow-colored cyan couplers and the couplers represented by the general formula (A) were altered as set forth in Table 3.
  • Specimen 211 was prepared in the same manner as Specimen 101, except that the amount of CM-1 incorporated in the 6th layer and CM-2 incorporated in the 8th layer were each halved and the yellow-colored cyan coupler incorporated in the red-sensitive emulsion layer and the coupler represented by the general formula (A) were altered as set forth in Table 3.
  • Specimens 201 to 211 thus prepared were then measured for color stain ( ⁇ Dy) in cyan images in accordance with the method described in Example 1. These specimens were exposed to light through a green separation filter. The density value measured by blue light was determined at the exposure which gives a density of (minimum density + 1.0) on the characteristic curve obtained by the density measurement by green light. Color stain ( ⁇ D G ) in magenta images was determined by substracting from this value the minimum density measured by blue light. The smaller the absolute value is, the smaller is the color stain and the more advantageous is the color reproduction, as in Example 1. These specimens were also evaluated for preservability of the light-sensitive material as in Example 1. The results are set forth in Table 4.
  • the processing step used in this example will be set forth below.
  • the processing was effected by means of an automatic developing machine.
  • Specimen 201 which had been imagewise exposed to light was processed until the accumulated replenishment of the color developer reached three times the capacity of the running solution tank before the other specimens were processed.
  • the various processing solutions had the following compositions:
  • washing solution (The running solution was used also as replenisher)
  • Tap water was passed through a mixed bed column packed with an H-type strongly acidic cation exchange resin (Amberlite IR-120B available from Rohm & Haas) and an OH-type strongly basic anion exchange resin (Amberlite IRA-400 available from the same company) so that the calcium and magnesium ion concentrations were each reduced to 3 mg/t or less.
  • Dichlorinated sodium isocyanurate and sodium sulfate were then added to the solution in amounts of 20 mg/t and 150 mg/t, respectively.
  • the washing solution thus obtained had a pH value of 6.5 to 7.5.
  • Table 4 shows that the incorporation of the yellow-colored cyan couplers of the present invention in the red-sensitive emulsion layer provides a reduction in color stain in cyan images, higher color reproducibility and improved preservability of light-sensitive material.
  • Specimen 301 was prepared in the same manner as Specimen 112, except that the amount of ExM-7 incorporated in the 6th and 7th layers and ExM-8 incorporated in the 8th layer were each halved. Specimen 301 thus prepared was cut into 35-mm wide strips.
  • Specimens were also prepared in the same manner as Specimens 301, 101 and 112, except that the amount of chemical sensitizers and other additives, i.e., sensitizing dye and Cpd-7, incorporated during the preparation of emulsions were altered so that these specimens exhibited the same sensitivity and gradation without altering the coated amount of silver.
  • chemical sensitizers and other additives i.e., sensitizing dye and Cpd-7
  • the Macbeth charts, chromaticity diagrams and patterns were printed on a color paper (Super FA, available from Fuji Photo Film) through these color negative films by a printer processor PP-400 (Fuji Photo Film).
  • the color paper was then processed in accordance with CP-40 processing (Fuji Photo Film).
  • Specimens 301 and 101 took almost the same period of time for exposure.
  • Specimen 112 took a slightly longer time for exposure than Specimen 301.
  • Specimens 301 and 112 were better than Specimen 101, particularly in the hue of yellow to red.
  • Specimen 401 was prepared in the same manner as Specimen 201 in Example 2 in JP-A-1-269935.
  • Specimen 402 was prepared in the same manner as in Specimen 401, except that EX-3 incorporated in the 2nd, 3rd and 4th layers was replaced by the yellow-colored cyan coupler (YC-7) in equimolar amounts, respectively.
  • YC-7 yellow-colored cyan coupler
  • Specimen 402 comprising the yellow-colored cyan coupler of the present invention provides better results in sensitivity of cyan density, preservability of light-sensitive material and stability of latent images than does Specimen 401. This shows that the yellow-colored cyan couplers of the present invention are excellent.
  • a multilayer color light-sensitive material Specimen 501 was prepared by coating on an undercoated cellulose triacetate film support the following layers.
  • the figures indicate the coated amount of each component in g/m 2 .
  • the coated amount of silver halide and colloidal silver are represented in terms of the amount of silver.
  • the coated amount of sensitizing dye is represented in a mol amount per mol of silver halide contained in the same layer.
  • 3rd layer 1st red-sensitive emulsion layer
  • 5th layer 3rd red-sensitive emulsion layer
  • 8th layer 2nd green-sensitive emulsion layer
  • llth layer 1st blue-sensitive emulsion layer
  • all these layers further comprised W-1, W-2, W-3, B-4, B-5, F-1, F-2, F-3, F-4, F-5, F-6, F-7, F-8, F-9, F-10, F-1, F-12, F-13, F-14, iron salts, lead salts, gold salts, platinum salts, iridium salts, and rhodium salts.
  • the silver halide emulsions used are set forth in Table 5.
  • Specimen 502 was prepared in the same manner as Specimen 501, except that the yellow-colored cyan coupler (YC-85) was coated on the 3rd, 4th and 5th layers in the amounts of 0.06 g/m 2 , 0.05 g/m 2 , and 0.02 g/m 2 , respectively, EX-6 incorporated in the 7th layer was replaced by Coupler [A-4]-48 in an equimolar amount (as calculated in terms of EX-6), EX-6 incorporated in the 8th layer was replaced by Coupler [A-4]-48 in half the equimolar amount, EX-11 incorporated in the 9th layer was replaced by Coupler [A-4]-51 in an equimolar amount, and HBS-3 incorporated in the 7th and 8th layer was omitted.
  • the yellow-colored cyan coupler YC-85
  • Specimens 503 to 510 were prepared in the same manner as Specimen 502 exept that the yellow-colored cyan coupler YC-85 incorporated in the red-sensitive emulsion layer in the 3rd, 4th and 5th layers, Couplers [A-4]-48 and [A-4]-51 incorporated in the green-sensitive emulsion layer in the 7th, 8th and 9th layers, and EX-8 and EX-10(D-25) incorporated in the 3rd, 4th, 7th, 8th, 11th, and 12th layers were replaced by the compounds set forth in Tables 6 and 7 in equimolar amounts, respectively.
  • the specimens were exposed to light through an MTF pattern. The MTF value was then determined.
  • the MTF values of the cyan and magenta dyes are set forth in Table 7.
  • the specimens were exposed to white light, and then processed to obtain color images. Characteristic curves were obtained from the color images by blue light, green light and red light. These specimens were stored at a temperature of 80 C and a relative humidity of 70% for 7 days. After the test, these specimens were again measured for density, and the density was determined at the exposure which gives a density of (minimum density developed before test + 1.5). The percentage of the density (D%) was determined with respect to the value obtained before test. The nearer to 100 the value is, the more fast is the color image.
  • Table 8 shows that the combination of the yellow-colored cyan couplers and the couplers of the general formula (A), with the additional use of the compounds of the general formula (I), provides improvements in sharpness as well as in color image fastness, particularly in yellow dye images, but also in magenta dye images. This provides improvements in inhibition of deterioration of the three colors, i.e., yellow, magenta and cyan images.
  • the comparison between Specimens 507 to 509 and Specimens 502 to 506 shows that the three color images of substantially the same level exhibit relatively uniform fastness.
  • the combination of the yellow-colored cyan couplers and the pyrazoloazole couplers of the general formula (A) provides improvements in color reproducibility and high sensitivity as well as improvements in preservability of light-sensitive material and stability of latent images.
  • the use of the pyrazoloazole couplers reduces the amount of the yellow-colored magenta couplers to be used in combination with the conventional 5-pyrazolone couplers.
  • the present invention provides a silver halide color photographic material which exhibits an excellent color reproducibility and preservability.
  • the use of the compounds represented by the general formula (I) provides improvements in color image fastness. This improves the inhibition of deterioration of yellow, magenta and cyan images. Thus, all the three color images exhibit uniform fastness. This further improves the color reproducibility.
  • the present invention also provides a silver halide color photographic material which exhibits improved color image fastness.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
EP91107617A 1990-05-10 1991-05-10 Farbphotographisches Silberhalogenidmaterial Withdrawn EP0456257A1 (de)

Applications Claiming Priority (4)

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JP12082090 1990-05-10
JP120820/90 1990-05-10
JP3036568A JP2678825B2 (ja) 1990-05-10 1991-02-07 ハロゲン化銀カラー写真感光材料
JP36568/91 1991-02-07

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0551130A1 (de) * 1992-01-10 1993-07-14 Fuji Photo Film Co., Ltd. Farbphotographisches lichtempfindliches Silberhalogenidmaterial
EP0570923A1 (de) * 1992-05-19 1993-11-24 Fuji Photo Film Co., Ltd. Farbphotographisches lichtempfindliches Silberhalogenidmaterial
EP0574927A1 (de) * 1992-06-18 1993-12-22 Fuji Photo Film Co., Ltd. Farbphotographisches lichtempfindliches Silberhalogenidmaterial
EP0724194A1 (de) 1995-01-30 1996-07-31 Fuji Photo Film Co., Ltd. Farbphotographisches Silberhalbgenid-Material
EP1582919A1 (de) 2004-03-23 2005-10-05 Fuji Photo Film Co. Ltd. Lichtempfindliches Silberhalogenidmaterial und photothermographisches Material
EP1635216A1 (de) 2004-09-14 2006-03-15 Fuji Photo Film Co., Ltd. Photothermographisches Material
EP1754758A2 (de) 2005-08-17 2007-02-21 Fuji Photo Film Co., Ltd. Tintenzusammensetzung enthaltend ein Oniumsalz und eine kationisch polymerisierbare Verbindung, Tintenstrahldruckverfahren, bedrucktes Material, Verfahren zur Herstellung einer lithographischen Druckplatte, und lithographische Druckplatte
EP2145931A1 (de) 2008-07-16 2010-01-20 Fujifilm Corporation Lichthärtbare Zusammensetzung, Tintenzusammensetzung und Tintenstrahlaufzeichnungsverfahren mit der Tintenzusammensetzung
EP2169021A1 (de) 2008-09-25 2010-03-31 Fujifilm Corporation Tintenzusammensetzung, Tintenstrahlaufzeichnungsverfahren und gedrucktes Material
EP2385425A1 (de) 2010-05-07 2011-11-09 Fujifilm Corporation Photographisches lichtempfindliches Silberhalogenidmaterial für Kino
WO2025058077A1 (ja) 2023-09-15 2025-03-20 富士フイルム株式会社 化合物、組成物、機能性材料、ハロゲン化銀写真感光材料、及び、拡散転写型ハロゲン化銀写真感光材料

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63304242A (ja) * 1987-06-04 1988-12-12 Fuji Photo Film Co Ltd 熱現像カラ−感光材料
US4824772A (en) * 1985-12-26 1989-04-25 Fuji Photo Film Co., Ltd. Silver halide color photographic material containing pyrazoloazole coupler and DIR compound
EP0318992A2 (de) * 1987-12-01 1989-06-07 Fuji Photo Film Co., Ltd. Farbphotographisches Silberhalogenidmaterial und Verfahren zur Behandlung
DE3815469A1 (de) * 1988-05-06 1989-11-16 Agfa Gevaert Ag Farbfotografisches aufzeichnungsmaterial mit neuen farbigen blaugruenkupplern

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4824772A (en) * 1985-12-26 1989-04-25 Fuji Photo Film Co., Ltd. Silver halide color photographic material containing pyrazoloazole coupler and DIR compound
JPS63304242A (ja) * 1987-06-04 1988-12-12 Fuji Photo Film Co Ltd 熱現像カラ−感光材料
EP0318992A2 (de) * 1987-12-01 1989-06-07 Fuji Photo Film Co., Ltd. Farbphotographisches Silberhalogenidmaterial und Verfahren zur Behandlung
DE3815469A1 (de) * 1988-05-06 1989-11-16 Agfa Gevaert Ag Farbfotografisches aufzeichnungsmaterial mit neuen farbigen blaugruenkupplern

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 6, no. 217 (P-152)(1095) 30 October 1982, & JP-A-57 122434 (KONISHIROKU) 30 July 1982, *

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0551130A1 (de) * 1992-01-10 1993-07-14 Fuji Photo Film Co., Ltd. Farbphotographisches lichtempfindliches Silberhalogenidmaterial
US5380631A (en) * 1992-01-10 1995-01-10 Fuji Photo Film Co., Ltd. Silver halide color photographic light-sensitive material
EP0570923A1 (de) * 1992-05-19 1993-11-24 Fuji Photo Film Co., Ltd. Farbphotographisches lichtempfindliches Silberhalogenidmaterial
US5370979A (en) * 1992-05-19 1994-12-06 Fuji Photo Film Co., Ltd. Silver halide color photographic light-sensitive material
EP0574927A1 (de) * 1992-06-18 1993-12-22 Fuji Photo Film Co., Ltd. Farbphotographisches lichtempfindliches Silberhalogenidmaterial
US5376515A (en) * 1992-06-18 1994-12-27 Fuji Photo Film Co., Ltd. Silver halide color photographic light-sensitive material
EP0724194A1 (de) 1995-01-30 1996-07-31 Fuji Photo Film Co., Ltd. Farbphotographisches Silberhalbgenid-Material
EP1582919A1 (de) 2004-03-23 2005-10-05 Fuji Photo Film Co. Ltd. Lichtempfindliches Silberhalogenidmaterial und photothermographisches Material
EP1635216A1 (de) 2004-09-14 2006-03-15 Fuji Photo Film Co., Ltd. Photothermographisches Material
EP1754758A2 (de) 2005-08-17 2007-02-21 Fuji Photo Film Co., Ltd. Tintenzusammensetzung enthaltend ein Oniumsalz und eine kationisch polymerisierbare Verbindung, Tintenstrahldruckverfahren, bedrucktes Material, Verfahren zur Herstellung einer lithographischen Druckplatte, und lithographische Druckplatte
EP2145931A1 (de) 2008-07-16 2010-01-20 Fujifilm Corporation Lichthärtbare Zusammensetzung, Tintenzusammensetzung und Tintenstrahlaufzeichnungsverfahren mit der Tintenzusammensetzung
EP2169021A1 (de) 2008-09-25 2010-03-31 Fujifilm Corporation Tintenzusammensetzung, Tintenstrahlaufzeichnungsverfahren und gedrucktes Material
EP2385425A1 (de) 2010-05-07 2011-11-09 Fujifilm Corporation Photographisches lichtempfindliches Silberhalogenidmaterial für Kino
WO2025058077A1 (ja) 2023-09-15 2025-03-20 富士フイルム株式会社 化合物、組成物、機能性材料、ハロゲン化銀写真感光材料、及び、拡散転写型ハロゲン化銀写真感光材料

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