Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • 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
  • G03C7/392—Additives
  • G03C7/39208—Organic compounds
  • G03C7/39212—Carbocyclic
  • G03C7/39216—Carbocyclic with OH groups

Definitions

• This invention relates to a silver halide color light-sensitive material and, more particularly, to a photographic material having improved sharpness and reduced color stain and color fog, as well as to light-­sensitive materials having improved graininess.
• 2-Equivalent couplers have been proposed for various purposes: reducing the thickness of emulsion layers by enhancing the color-forming efficiency of couplers in light-sensitive materials; improving image sharpness by reducing blurring which is caused by light scattering; reducing the amount of silver; and increasing sensitivity.
• Such 2-equivalent couplers have been put into use, as described in T. H. James; The Theory of the Photographic Process , Chap. 12 (4th ed. MacMillan Co.). While these 2-equivalent couplers can reduce the thickness of emulsion layers and the amount of silver required, they involve certain disadvantages.
• hydroquinone compounds as quinonediimine scavengers.
• Japanese Patent Application (OPI) No. 22,237/82 proposes a hydroquinone nucleus substituted with an electron attractive group such as an acyl group, a nitro group, a cyano group, a formyl group, a halogenated alkyl group, etc. These possess excellent color stain-­preventing ability, but still have the disadvantage that they produce colored materials; that they deteriorate during preparation and storage of light-sensitive materials, and that they fog silver halide emulsions.
• Japanese Patent Publication No. 7578/80 discloses compounds containing in the same molecule both a hydroquinone residue analogous to the compounds of the present invention and a coupler residue. However, these compounds form color image by a coupling reaction during development processing, thus failing to prevent color stain.
• An object of the present invention is to provide a light-sensitive material having excellent sharpness.
• Another object of the present invention is to provide a light-sensitive material undergoing less color stain and less color fog and providing excellent color reproduction.
• a further object of the present invention is to provide a light-sensitive material having high sensitivity and forming a high contrast image.
• Still a further object of the present invention is to provide a light-sensitive material having excellent graininess.
• Still a further object of the present invention is to provide a light-sensitive material which does not deteriorate (with respect to sensitivity and increase of fog) during preparation and storage.
• Still a further object of the present invention is to provide a less costly light-sensitive material containing a reduced amount of silver.
• a silver halide photographic material composed of a support having thereon a red-sensitive silver halide emulsion layer containing a cyan coupler, a green-­ sensitive silver halide emulsion layer containing a magenta coupler, a blue-sensitive silver halide emulsion layer containing a yellow coupler, at least one of the light-sensitive silver halide emulsion layers containing a 2-equivalent coupler; at least one light-­insensitive layer containing at least one of compound represented by formula (I), bis- and tris-compounds and polymers derived therefrom, and an alkali-labile precursor thereof (hereinafter all of these compounds are referred to "compounds represented by formula (I)”): wherein R1 and R2 each represents a hydrogen atom, a halogen atom, -SO3M, -COOM (wherein M represents H, alkali metal atom or -
• the light-insensitive layers containing the compounds represented by general formula (I) are preferably in close proximity to the 2-­equivalent coupler-containing emulsion layers.
• the term "in close proximity" as used herein means a directly adjacent layer or a layer separated by a single light-­insensitive layer.
• Alkali-labile precursors of the compounds of the present invention represented by general formula (I) are compounds in which the hydroxy groups at the 1- and 4-positions of the hydroquinone skeleton in the compound represented by general formula (I) is protected by a group capable of being cleaved under alkaline conditions of a developing process.
• the light-insensitive layer may contain a silver halide emulsion that is not chemically sensitized, a fine-­grain silver halide emulsion, and/or colloidal silver grains.
• the light-insensitive layer may be a protective layer, an inter layer, a filter layer, an antihalation layer or a layer specifically provided for incorporating the compound.
• a hydrophilic material which is usually used as a binder in a photographic material (e.g., gelatin, a synthetic hydrophilic polymer) may be used.
• the light-insensitive layer containing the compound of general formula (I) may be provided in any position in a light-sensitive material as long as it is in close proximity to a 2-equivalent coupler-containing emulsion layer.
• it is provided between emulsion layers having different color sensitivities or between two emulsion layers having substantially the same color sensitivity and, more preferably, between a layer having the maximum sensitivity in a color sensitive layer unit and a layer sensitive in different color and having the minimum sensitivity, between layers one having a higher sensitivity and the other having a lower sensitivity and a each having substantially the same color sensitivity, or between layers one having a intermediate sensitivity and the other having a lower or a higher sensitivity and each having substantially the same color sensitivity.
• the compound of the present invention represented by the general formula (I) can be added to a light-­sensitive material in the same manner as for dispersing and adding couplers as described hereinafter.
• These compounds are added to layers in close proximity to 2-equivalent couplers in a total amount of about 0.005 to 2.0 g/m2, preferably about 0.01 to 1.0 g/m2, more preferably about 0.03 to 0.3 g/m2.
• the thickness of the light-insensitive layer such as protective layer, an inter layer, a filter layer and an antihalation layer generally is from about 0.05 to 2.0 ⁇ m, preferably from about 0.1 to 1.5 ⁇ m, and more preferably from about 0.2 to 1.0 ⁇ m.
• the thickness of the layer containing the compound is generally from about 0.1 to 2.0 ⁇ m, preferably from about 0.2 to 1.5 ⁇ m, and more preferably from about 0.3 to 1.0 ⁇ m.
• 2-equivalent couplers used in the present invention are preferably added to layers in close proximity to light-insensitive layers to which the compounds of the present invention are added.
• the color-sensitive layers to which they are added are constituted by two layers having different light-­sensitivities, it is preferred to add them at least to the less sensitive layer thereof, and, when constituted by three layers, at least to the least sensitive layer or to the least and the intermediate sensitivity layers.
• the 2-­equivalent coupler is usually added in an amount of from about 0.01 to 2.0 g/m2, preferably from about 0.03 to 1.5 g/m2, and more preferably from about 0.05 to 1.2 g/m2.
• the ratio of the amount of the 2-equivalent coupler to the amount of the compound is preferably about 0.001 to 100, and more preferably about 0.05 to 2.0 by weight.
• each of the acylamino group, sulfonyl group, and sulfamoyl group may be comprised of either aliphatic (C1 ⁇ C32), alicyclic (C4 ⁇ C32), aromatic (C6 ⁇ C32) or heterocyclic (C1 ⁇ C32) atomic group
• each of acyl group and carbamoyl group may be comprised of either aliphatic (C2 ⁇ C32), alicyclic (C5 ⁇ C32) aromatic (C7 ⁇ C32) or heterocyclic (C2 ⁇ C32) atomic group.
• R1 and R2 which may be the same or different, each represents hydrogen atom, a halogen atom (e.g., a chlorine atom, a bromine atom), -SO3M, -COOM (wherein M represents H, an alkali metal atom or -NH4), an alkyl group (C1 ⁇ C32; e.g., a methyl group, a pentadecyl group, a t-hexyl group, etc.), an acylamino group (C1 ⁇ C32; e.g., an acetylamino group, a benzoylamino group, etc.), an alkoxy group (C1 ⁇ C32; e.g., a methoxy group, a butoxy group, etc.), an aryloxy group (C6 ⁇ C32; e.g., a phenoxy group, etc.), an alkylthio group (C1 ⁇ C32; e.g.,
• an alkyl group, an acylamino group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a sulfonyl group, an acyl group, a carbamoyl group, and a sulfamoyl group may be substituted or unsubstituted.
• substituents for the alkyl group, the alkoxy group, the aryloxy group, the alkylthio group, the arylthio group, the sulfonyl group, the acyl group include groups recited above as R1 and R2, and examples for substituents for the carbamoyl group and the sulfamoyl group include an alkyl group and aryl group.
• X represents -CO- or -SO2-.
• R3 represents an alkyl group (C1 ⁇ C32; e.g., a heptadecyl group, a 1-hexylnonyl group, a 1-(2,4-di-t-­amylphenoxy)propyl group, etc.), an aryl group (C6 ⁇ C32; e.g., a phenyl group, a 3,5-bis(2-hexyldecanamido)phenyl group, a 3,4-bis(hexadecyloxycarbonyl)phenyl group, a 2,4-bis(tetradecyloxy)phenyl group, etc.), a heterocyclic group, preferably 5- to 7-membered heterocyclic group having at least one of N, O and S atom as a hetero atom, such as, a pyridinyl group, a pyrrolidinyl group piperidinyl group, a 2-thienyl group, a 2-furyl group,
• substituents include a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, a carbonamido group, a sulfonamido group, an alkylthio group, an arylthio group, an aryl group, an alkoxycarbonyl group, and a carbamoyl group, and these groups may be further substituted with such groups.
• the sum of the carbon atoms contained in R1, R2, and R3 should be 10 or more to provide non-diffusibility to the compound.
• the sum of the carbon atoms preferably at least 15, and it is preferably not more than 64.
• the compounds of the general formula (I) may be linked at at least one of R1, R2 and R3 to form a bis compound, a tris compound or a polymer thereof.
• R1 and R2 preferably each represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or an alkylthio group. Of these, a hydrogen atom, a halogen atom, and an alkyl group are more preferred, and a hydrogen atom is most preferred.
• preferred R3 groups include an alkyl group and an aryl group, with an aryl group being most preferred.
• R3 in the general formula (I) represents an aryl group
• substituents for the aryl group are not particularly limited, and preferred substituents include: a halogen atom, an alkyl group, an amido group, a sulfonamido group, an alkoxy group, an alkoxycarbonyl group, and a carbamoyl group.
• the aryl group preferably does not contain a sulfo group (-SO3M), a carboxyl group (-COOM), or other such water-soluble group, because these groups can adversely affect preservability of light-sensitive materials.
• the compounds used in the present invention are agents for preventing color stain and color fog in photographic light-sensitive materials, good color reproduction of the photographic light-sensitive materials is adversely affected if the compounds themselves is colored or form a color image in the course of development processing. According, the compounds of the present invention must first be substantially colorless.
• substantially colorless as used herein means not having an absorption of 5,000 or more in molar extinction coefficient in the visible wavelength region from 400 nm to 700 nm.
• the compounds to be used in the present invention must not possess within the molecule coupler residues capable of undergoing a coupling reaction with an oxidation product of a color developing agent to form color image (e.g., an acylacetanilide residue, a 5-­ pyrazolone residue, a 1-naphthol residue, etc.) and therefore do not form a color image by a coupling reaction in the development processing step.
• a color developing agent e.g., an acylacetanilide residue, a 5-­ pyrazolone residue, a 1-naphthol residue, etc.
• Typical examples of the protective group include an acyl group (e.g., an acetyl group, a chloroacetyl group, a benzoyl group, an ethoxy-carbonyl group, etc.) and a ⁇ -eliminatable group (e.g., a 2-cyanoethyl group, a 2-methanesulfonylethyl group, a 2-toluenesulfonylethyl group, etc.).
• an acyl group e.g., an acetyl group, a chloroacetyl group, a benzoyl group, an ethoxy-carbonyl group, etc.
• a ⁇ -eliminatable group e.g., a 2-cyanoethyl group, a 2-methanesulfonylethyl group, a 2-toluenesulfonylethyl group, etc.
• the compounds of the present invention represented by general formula (I), bis-, tris-compounds and polymers derived therefrom, and the alkali-labile precursors thereof can be readily synthesized according to processes described in U.S. Pat. 2,701,197, Japanese Patent Publication No. 37,497/84 (corresponding to U.S. Pat. 4,198,239) and Japanese Patent Application (OPI) No. 202,465/84 (corresponding to U.S. Pat. 4,584,264).
• Couplers used in the present invention are represented by the following general formuale (Cp-1) to (Cp-9).
• R51 represents an aliphatic group, an aromatic group, an alkoxy group or a heterocyclic group
• R52 and R53 which may be the same or different each represents an aromatic group or a heterocyclic gruop.
• the aliphatic group represented by R51 contains preferably 1 to 22 carbon atoms, and may be substituted or unsubstituted, and may be in a chain form or cyclic form.
• Substituents for an alkyl group represented by R51 include an alkoxy group, an aryloxy group, an amino group, an acylamino group, a halogen atom, etc.,which themselves may further be substituted.
• aliphatic group represented by R51 examples include an isopropyl group, an isobutyl group, a tert-butyl group, an isoamyl group, a tert-amyl group, a 1,1-dimethylbutyl, 1,1-­dimethylhexyl, 1,1-diethylhexyl gruop, a dodecyl group, a hexadecyl group, an octadecyl group, a cyclohexyl group, a 2-methoxyisopropyl group, a 2-phenoxyisopropyl group, 2-p-tert-butyl-­phenoxy-isopropyl group, an ⁇ -aminoisopropyl group, an ⁇ -(diethylamino­isopropyl group,an ⁇ -(succinimido)isopropyl group, an ⁇ -(phthalimido)isopropyl group
• R51, R52 or R53 represents an aromatic group (particularly a phenyl group)
• the aromatic group may be substituted, by an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an alkoxycarbonyl­amino group, an aliphatic amido group, an alkylsulfamoyl group, an alkylsulfonamido group, an alkyureido group, an alkyl-substituted succinimido group, etc., containing up to 32 carbon atoms.
• the alkyl group may contain in its chain an aromatic group such as a phenylene group.
• the phenyl group in the aromatic group may also be substituted by an aryloxy group, an aryloxycarbonyl group, an arylcarbamoyl group, an arylamido group, an arylsulfamoyl group, an arylsulfonamido group, an arylureido group, etc., with the aryl moiety of these substituents being optionally substituted by one or more alkyl groups containing a total of 1 to 22 carbon atoms.
• the phenyl group in the aromatic group represented by R51, R52 or R53 may further be substituted by an amino group including those substituted by a lower alkyl group or groups containing 1 to 6 carbon atoms, a hydroxyl group, a carboxyl group, a sulfo group, a nitro group, a cyano group, a thiocyano group or a halogen atom.
• R51, R52 or R53 may represent a substituent in which a phenyl group is fused with an other ring, such as a naphthyl group, a quinolyl group, an isoquinolyl group, a chromanyl group, a coumaranyl group, a tetrahydronaphthyl group, etc. These substituents themselves may further have a substituent or substituents.
• the alkyl moiety includes a straight or branched alkyl, alkenyl, cyclic alkyl or cyclic alkenyl group containing 1 to 32, preferably 1 to 22, carbon atoms, which may further be substituted by a halogen atom, an aryl group, an alkoxy group, etc.
• R51, R52 or R53 represents a heterocyclic group
• the heterocyclic group is linked to the carbon atom of the carbonyl group in the acyl group of the ⁇ -acylacetamido group, or to the nitrogen atom of the amido group of the ⁇ -acylacetamido group, through one carbon atom contained in the ring.
• Such hetero rings include thiophene, furan, pyran, pyrrole, pyrazole, pyridine, pyrazine, pyrimidine, pyridazine, indolidine, imidazole, thiazole, oxazole, triazine, thiadiazine, oxazine, etc. These may further have a substituent or substituents in the ring.
• R55 represents a straight or branched alkyl group containing 1 to 32, preferably 1 to 22, carbon atoms (e.g., a methyl group, an isopropyl group, a tert-butyl group, a hexyl group, a dodecyl group, etc.), an alkenyl group (e.g., an allyl group, a cyclic alkyl group (e.g., a cyclopentyl group, a cyclohexyl group, a norbornyl group, etc.), an aralkyl group (e.g., a benzyl group, a ⁇ -phenylethyl group, etc.), or a cyclic alkenyl group (e.g., a cyclopentenyl group, a cyclohexenyl group, etc.), which may further be substituted by a halogen atom, a nitro group,
• R55 may represent an aryl group (e.g., a phenyl group, an ⁇ -or ⁇ -naphthyl group, etc.).
• the aryl group may have one or more substituents.
• substituents include an alkyl group, an alkenyl group, a cyclic alkyl group, an aralkyl group, a cyclic alkenyl group, a halogen atom, a nitro group, a cyano group, an aryl group, an alkoxy group, an aryloxy group, a carboxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfo group, a sulfamoyl group, a carbamoyl group, an acylamino group, a diacylamino group, a ureido group, a urethane group, a sulfonamido group, a heterocyclic
• R55 may represent a heterocyclic group (for example, a 5- or 6-membered heterocyclic group or fused heterocyclic group containing a sulfur atom, an oxygen atom or a nitrogen atom as a hetero atom, such as a pyridyl group, a quinolyl group, a furyl group, a benzo­thiazolyl group, an oxazolyl group, an imidazolyl group, a naphthoxazolyl group, etc.), a heterocyclic group substituted with a substituents for the aryl group represented by R55, an aliphatic or aromatic acyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkylcarbamoyl group, an arylcarbamoyl group, an alkylthiocarbamoyl group or an arylthiocarbamoyl group.
• a heterocyclic group for example, a 5-
• R54 represents a hydrogen atom, a straight or branched alkyl or alkenyl group containing 1 to 32, preferably 1 to 22, carbon atoms, a cyclic alkyl group, an aralkyl group, a cyclic alkenyl group (these groups optionaly having substituents mentioned with respect to R55), an aryl group and a heterocyclic group (these optionally having substituents mentioned with respect to R55), an alkoxycarbonyl group (e.g., a methoxycarbonyl group an ethoxycarbonyl group, a stearyloxycarbonyl group, etc.), an aryloxycarbonyl group (e.g., a phenoxycarbonyl group, a naphthoxycarbonyl group, etc.), an aralkyloxycarbonyl group (e.g., a benzyloxycarbonyl group, etc.), an alkoxy group (e.g., a methoxy group,
• R56 represents a hydrogen atom or a straight or branched chain alkyl or alkenyl group containing 1 to 32, preferably 1 to 22, carbon atoms, a cyclic alkyl group, an aralkyl group or a cyclic alkenyl group, which may be substituted by the substituents for R55.
• R56 may represent an aryl group or a heterocyclic group, which may be substituted by the substituents for R55.
• R56 may represent a cyano group, an alkoxy group, an aryloxy group, a halogen atom, a carboxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, a sulfo group, a sulfamoyl group, a carbamoyl group, an acylamino group, a diacylamino group, a ureido group, a urethane group, a sulfonamido group, an arylsulfonyl group, an alkylsulfonyl group, an arylthio group, an alkylthio group, an alkylamino group, a dialkyl­amino group, an anilino group, an N-arylanilino group, an N-alkylanilino group, an N-acylanilino group or a hydroxyl group.
• R56 may be substituted at any position of the benzen ring.
• R57, R58, and R59 which may be the same or different each represents a group present ordinary 4-equivalent phenolic or ⁇ -naphtholic couplers, specifically a hydrogen atom, a halogen atom, an alkoxy-­carbonylamino group, an aliphatic hydrocarbon group, an N-arylureido group, an acylamino group, -O-R62 or -S-R62 (provided that R62 represents an aliphatic hydrocarbon group).
• Plural R57 groups in the same molecule may be the same or different.
• the aliphatic hydrocarbon group includes those which have a substituent or substituents.
• the aryl moiety may have one or more substituent for R55.
• R58 and R59 include aliphatic hydrocarbon groups, aryl groups, and hetero ring groups, or one of them may be a hydrogen atom.
• the groups may have a substituent or substituents.
• R58 and R59 may be linked to form a nitrogen-containing hetero ring nucleus.
• the aliphatic hydrocarbon residue represented by R58 and R59 may be saturated or unsaturated, and may be in a straight chain form, a branched chain form or a cyclic form.
• Preferred examples thereof include an alkyl group (e.g., a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, an isobutyl group, a dodecyl group, an octadecyl group, a cyclobutyl group, a cyclohexyl group, etc.), and an alkenyl group (e.g., an allyl group, an octenyl group, etc.).
• an alkyl group e.g., a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group
• the aryl group represented by R58 and R59 includes a phenyl group, a naphthyl group, etc.
• the hetero ring group represented by R58 and R59 typically includes a pyridinyl group, a quinolyl group, a thienyl group, a piperidyl group, an imidazolyl group, etc.
• the substituents for these aliphatic hydrocarbon groups, aryl groups, and hetero ring groups include a halogen atom, a nitro group, a hydroxyl group, a carboxyl group, an amino group, a substituted amino group, a sulfo group, an alkyl group, an alkenyl group, an aryl group a heterocyclic group, an alkoxy group, an aryloxy group, an arylthio group, an arylazo group, an acylamino group, a carbamoyl group, an ester group, an acyl group, an acyloxy group, a sulfonamido group, a sulfamoyl group, a sulfonyl group, a morpholino group, etc.
• l represents an integer of 1 to 4
• m represents an integer of 1 to 3
• p represents an integer of 1 to 5.
• preferred yellow couplers are those represented by general formula (Cp-1), in which R51 represents a t-butyl group or a substituted or unsubstituted aryl group, and R52 represents a substituted or unsubstituted aryl group; and those represented by general formula (Cp-2), in which R52 and R53 each represents a substituted or unsubstituted aryl group.
• Preferred magenta couplers are those represented by general formula (Cp-3), in which R54 represents an acylamino group, a ureido group or an arylamino group and R55 represents a substituted aryl group; those represented by general formula (Cp-4) in which R54 represents an acylamino group, a ureido group or an arylamino group and R56 represents a hydrogen atom; and those represented by general formulae (Cp-5) and (Cp-6) in which R54 and R56 each represents a straight or branched alkyl or alkenyl group, a cyclic alkyl or aralkyl group or a cyclic alkenyl group.
• Preferred cyan couplers are those represented by general formula (Cp-7), in which R57 represents a 2-position acylamino or ureido group, a 5-position acylamino or alkyl group, or a 6-position hydrogen or chlorine atom; and those represented by general formula (Cp-9) in which R57 represents a 5-position hydrogen atom, acylamino group, sulfonamido group or alkoxycarbonyl group, R58 represents a hydrogen atom, and R59 represents a phenyl group, an alkyl group, an alkenyl group, a cyclic alkyl group, an aralkyl group or a cyclic alkenyl group.
• Z1 represents a halogen atom, a sulfo group, an acyloxy group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group or a heterocyclic thio group, which may be further substituted by such substitutents as an aryl group (e.g., a phenyl group), a nitro group, a hydroxyl group, a cyano group, a sulfo group, an alkoxy group (e.g., a methoxy group), an aryloxy group (e.g., a phenoxy group), an acyloxy group (e.g., an acetoxy group), an acylamino group (e.g., an acetylamino group), a sulfonamido group (e.g., a methanesulfonamido group), a aryl group (e
• Z2 and Y which may be the same or different each represents a coupling-off group bonded to the coupling site through an oxygen atom, a nitrogen atom or a sulfur atom.
• Z2 and Y are bonded to the coupling site through an oxygen atom, a nitrogen atom or a sulfur atom, these atoms are bound to an alkyl group, an aryl group, an alkylsulfonyl group, an arylsulfonyl group, an alkylcarbonyl group, an arylcarbonyl group or a heterocyclic group.
• Z2 or Y represents a 5- or 6-membered ring containing the nitrogen atom to form a coupling-off group, (e.g., an imidazolyl group, a pyrazolyl group, a triazolyl group, a tetrazolyl group, etc.).
• a coupling-off group e.g., an imidazolyl group, a pyrazolyl group, a triazolyl group, a tetrazolyl group, etc.
• the above-described alkyl, aryl, and hetorocyclic groups contained in Z2 and Y may have substituents.
• substituents include an alkyl group (e.g., a methyl group, an ethyl group, etc.), an alkoxy group (e.g., a methoxy group, an ethoxy group, etc.), an aryloxy group (e.g., a phenyloxy group, etc.), an alkoxycarbonyl group (e.g., a methoxycarbonyl group, etc.), an acylamino group (e.g., an acetylamino group, etc.), a carbamoyl group, an alkylcarbamoyl group (e.g., a methylcarbamoyl group, an ethylcarbamoyl group, etc.), a dialkylcarbamoyl group (e.g., a dimethl
• substituents include a halogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, and a cyano group.
• Z2 are groups which are bonded to the coupling site through a nitrogen atom or a sulfur atom
• preferred examples of Y are a chlorine atom and groups which are bonded to the coupling site through an oxygen atom, a nitrogen atom or a sulfur atom.
• Z3 represents a hydrogen atom or a group represented by the following general formulae (R-I), (R-II), (R-III) or (R-IV): R63 (R-I) wherein R63 represents substituted or unsubstituted aryl or heterocyclic group; wherein R64 and R 65, which may be the same or different, each represents a hydrogen atom, a halogen atom, a carboxylic acid ester group, an amino group, an alkyl group, an alkylthio group, an alkoxy group, an alkylsufonyl group, an alkylsulfinyl group, a carboxylic acid group, a sulfonic acid group, an unsubstituted or substituted phenyl or hetero cyclic group; wherein W1 represents a non-metallic atomic group necessary for forming a 4-, 5- or 6-membered ring together with therein.
• R66 and R67 which may be the same or different each represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group or a hydroxy group
• R68, R69, and R70 which may be the same or different, each represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group or an acyl group
• W2 represents an oxygen atom or a sulfur atom.
• 2-equivalent magenta couplers or 2-equivalent cyan couplers are preferably used, and especially 2-equivalent magenta coupers are preferably used.
• 2-Equivalent yellow couplers include the following examples, but the present invention is not to be consumed as being limited thereto.
• silver halides incorporated in the photographic emulsion layers of photogrpahic light-­sensitive materials of the present invention are silver bromoiodide, silver chloroiodide, and silver chlorobromoiodide containing up to about 30 mol % of silver iodide.
• a particularly preferable silver halide is silver bromoiodide containing about 2 to about 25 mol % of silver iodide.
• the silver halide grains to be used in the photographic emulsion may have a regular crystal form such as cubic, octahedral or tetradecahedral form, an irregular form such as a spherical form or tabular form, a form having crystal defect such as a twin plane, or a composite form thereof.
• fine grains of up to about 0.1 ⁇ m and large grains of from about 0.1 to 10 ⁇ m in projected area diameter may be used.
• Polydisperse emulsions and monodisperse emulsions may be used.
• the silver halide photographic emulsions used in the present invention may be prepared by the processes described in, for example, Research Disclosure (RD), No. 17643 (Dec., 1978), pp.22-23, "1. Emulsion preparation and types", ibid. , No. 18716 (Nov., 1979), p.648, P. Glafkides; Chimie et Physique Photographique (Paul Montel, 1967), G. F. Duffin; Photographic Emulsion Chemistry (Focal Press, 1966), V. L. Zelikman et al; Making and Coating Photographic Emulsion (Focal Press, 1964), etc. Monodisperse emulsions described in U.S. Pats. 3,574,628 and 3,655,394, British Pat. No. 1,413,748, etc. are also preferable.
• Tabular grains of about 5 or more in aspect ratio are also usable. Such tabular grains may be easily prepared according to processes described in Gutoff; Photographic Science and Engineering , vol. 14, pp.248-257 (1970), U.S. Pats. 4,434,226, 4,414,310, 4,433,048, 4,439,520, British Pat. No. 2,112,157, etc.
• the crystal structure of the silver halide grains may be a uniform structure, a structure wherein the inner portion and the outer portion are different from each other in halide composition, or a layered structure, or silver halide crystals different from each other may be joined to each other by epitaxial junction or, further, crystals joined to other compounds than silver halide such as silver rhodanide or lead oxide may be used.
• the silver halide emulsions are usually subjected to physical a ripening, chemical ripening, and spectral sensitization before use. Additives used in these steps are described in Research Disclosure Nos. 17643 and 18716. Places where such additives are described are summarized in the following Table.
• yellow couplers those described in, for example, U.S. Pats. 3,933,501, 4,022,620, 4,326,024, 4,401,752, Japanese Patent Publication No. 10739/83, British Pat. 1,425,020 and 1,476,760 are preferable.
• magenta couplers 5-pyrazolone type and pyrazoloazole type compounds are preferable, with those described in U.S. Pats. 4,310,619, 4,351,897, European Pat. No. 73,636, U.S. Pats. 3,061,432, 3,725,067, Research Disclosure No. 24,220 (June 1984), Japanese Patent Application (OPI) No. 33,552/85, Research Disclosure No. 24230 (June 1984), Japanese Patent Application (OPI) No. 43,659/85, U.S. Pats, 4,500,630, 4,540,654, being particularly preferred.
• Cyan couplers include phenolic and naphtholic couplers, and those described in U.S. Pats, 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, West German Patent Application (OLS) No. 3,329,729, European Pat. No. 121,365A, U.S. Pats. 3,446,622, 4,333,999, 4,451,559, 4,427,767, European Pat. No. 161,626A are preferred.
• colored couplers for correcting unnecessary absorption of colored dyes those which are described in Research Disclosure No. 17643, Item VII-G, U.S. Pats. 4,163,670, Japanese Patent Publication No. 39,413/82, U.S. Pats, 4,004,929, 4,138,258, and British Pat. No. 1,146,368 are preferred.
• couplers capable of forming colored dyes with a suitable controlled diffusibility those which are described in U.S. Pat. 4,366,237, British Pat. No. 2,125,570, European Pat. No. 96,570, West German Patent Application (OLS) No. 3,234,533 are preferred.
• Couplers capable of releasing a photographically useful group upon a coupling reaction are also preferably used in the present invention.
• DIR couplers capable of releasing a development inhibitor those which are described patents referred to in the foregoing RD 17643, Item VII-F; Japanese Patent Application (OPI) Nos. 151,944/82, 154,234/82, 184,248/85, and U.S. Pat. 4,248,962 are preferred.
• Preferred couplers capable of imagewise releasing a nucleating agent or a development accelerator include those described in British Pat. Nos. 2,097,140, 2,131,188, and Japanese Patent Application (OPI) Nos. 157,638/84, and 170,840/84.
• couplers used in the light-sensitive material of the present invention include competing couplers described in U.S. Pat. 4,130,427; polyequivalent couplers described in U.S. Pats. 4,283,472, 4,338,393, and 4,310,618; DIR redox compound-releasing couplers described in Japanese Patent Application (OPI) No. 185,950/85; couplers capable of re-acquiring color after being released described in European Pat. No. 173,302A, and the like.
• the couplers used in the present invention may be introduced into light-sensitive materials by various known processes.
• Suitable supports to be used in the present invention are described in, for example, the above Research Disclosure No. 17643, pp. 28; and id. No. 18716, p. 647, right col. to p. 648, left col.
• the color photographic material in accordance with the present invention may be development processed according to common processes described in the foregoing Research Disclosure No. 17643, pp. 28 - 29; and id. No. 18716, p. 651, left col. to right col.
• the color developer used for developing the light-sensitive material of the present invention is generally an alkaline aqueous solution containing an aromatic primary amine color-developing agent as a major component.
• an aromatic primary amine color-developing agent p-­phenylenediamine compounds are preferably used, although aminophenol compounds are also useful.
• Typical examples of the p-phenylenediamine compounds include 3-methyl-4-­amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -­hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -­methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-­N- ⁇ -methoxyethylaniline, and sulfates, hydrochlorides, and p-toluenesulfonates thereof. These compounds may be used as a combination of two or more depending upon the particular material.
• the color developer generally contains a pH buffer such as a carbonate, borate or phosphate of an alkali metal; and a development inhibitor or antifoggant such as a bromide, an iodide, a benzimidazole, a benzothiazole or a mercapto compound.
• a pH buffer such as a carbonate, borate or phosphate of an alkali metal
• a development inhibitor or antifoggant such as a bromide, an iodide, a benzimidazole, a benzothiazole or a mercapto compound.
• various preservatives e.g., hydroxylamine, diethylhydroxylamine, hydrazine sulfates, phenylsemicarbazides, triethanolamine, catecholsulfonic acids, triethylenediamines (e.g., 1,4-­diazabicyclo (2,2,2)-octane), etc.); organic solvents (e.g., ethylene glycol, diethylene glycol, etc.); development accelerators (e.g., benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines, etc.); dye-forming couplers; competing couplers; fogging agents (e.g., sodium borohydride, etc.); auxiliary developing agents (e.g., 1-phenyl-3-pyrazolidone, etc.); viscosity-increasing agents; various chelating agents such as aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, and phosphoric acid
• black-and-white developing agents such as dihydroxybenzenes (e.g., hydroquinone, etc.); 3-­pyrazolidones (e.g., 1-phenyl-3-pyrazolidone); or aminophenols (e.g., N-methyl-p-aminophenol) may be used alone or in combination.
• the color developer and the black-and-white developer generally have a pH of about 9 to 12.
• Bleaching may be conducted separately or simultaneously with fixing (bleach-fixing processing). In order to accelerate the processing, bleaching may be followed by bleach-fixing processing. Further, processing using two continuous bleach-fixing baths, processing in which fixing is conducted before bleach-fixing, and processing in which bleaching is conducted after bleach-­fixing may optionally be employed depending upon.
• Bleaching agents include for example, compounds of polyvalent metals such as iron(III), cobalt(III), chromium(VI), copper(II), etc., peracids, quinones, nitro compounds, etc.
• Typical bleaching agents used include ferricyanides; dichromates; organic complex salts of iron(III) or cobalt(III) such as complex salts of aminopolycarboxylic acids (e.g., ethylenediaminetetra­acetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, etc.) or organic acids (e.g., citric acid, tartaric acid, malic acid, etc.); persulfates; formates; permanganates; nitrobenzenes; etc.
• aminopolycarboxylic acids e.g., ethylenediaminetetra­acetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diamino
• iron(III) aminopolycarboxylate complex salts including iron(III) ethylenediaminetetraacetate and persulfates are preferred form the standpoint of rapid processing and prevention of environmental pollution. Further, iron(III) aminopolycarboxylate complex salts are particularly useful in both bleaching solutions and bleach-fixing solutions.
• the bleaching or bleach-fixing solutions containing these iron(III) aminopolycarboxylate complex sales usually have a pH or about 5.5 to 8 but, in order to accelerate the processing, the solution may be a lower pH.
• Bleaching accelerators may be used in the bleaching solution, bleach-fixing solution, and pre-baths thereof as desired.
• useful bleaching accelerators include mercapto group- or disulfido group-­containing compounds described in U.S. Pat. 3,893,858, West German Patent Nos. 1,290,812, 2,059,988, Japanese Patent Application (OPI) Nos. 32,736/78, 57,831/78, 37,418/78, 72,623/78, 95,630/78, 95,631/78, 104,232/78, 124,424/78, 141/623/78, 28,426/78, Research Disclosure , No.
• Fixing agents include thiosulfates, thiocyanates, thioether compounds, thioureas, a large amount of iodide salt, etc. Of these, thiosulfates are commonly used, with ammonium thiosulfate being most widely used. As preservatives for bleach-fixing solutions, sulfites, bisulfites or carbonyl-bisulfurous acid adducts are preferable.
• the silver halide color photographic light-sensitive material of the present invention After being subjected to the bleaching and fixing the silver halide color photographic light-sensitive material of the present invention is generally subjected to water-washing and/or a stabilizing step. Further, the light sensitive material of the present invention may be processed directly with a stabilizing solution in place of the above-described washing water. In such stabilizing processing, all of the techniques described in Japanese Patent Application (OPI) Nos. 8,543/82, 14,834/83, and 220,345/85 may be employed.
• OPI Japanese Patent Application
• the water-washing step is in some cases followed by stabilizing.
• An example thereof is a stabilizing bath containing formalin and a surfactant, which is used as a final bath for processing color light-­sensitive materials for photographic use.
• Various chelating agents and anti-fungal agents may also be added to this stabilizing bath.
• the various processing solutions are used at temperatures of about 10°C to 50°C. usually, temperatures of about 33°C to 38°C are standard, but higher temperatures may be employed for accelerating the processing and shortening processing times or lower temperatures may be employed to improve image quality and the stability of processing solutions.
• a multi-layer color light-sensitive material, sample 101, was prepared by multi-coating the layers of the following formulations of a subbed cellulose triacetate film support.
• the numerical values refer to the respective components as coated amounts in terms of g/m2.
• the numerical values refer to the amounts of coated silver and, for sensitizing dyes, the numerical values refer to the amounts of coted dye per mol of silver halide contained in the same layer.
• gelatin hardener H-1 In addition to the above-described ingredients, gelatin hardener H-1, and surfactant were added to each of the layers.
• Samples 102 to 136 were prepared by replacing the couplers used in the 5th and the 7th layers of sample 101 by equimolar amounts of the couplers shown in Table 1 and adding to the 6th layer the additives shown in Table 1.
• A-1, compound (13) of the present invention, and HBS-1 each added to the composition of the 6th layer in an amount of 0.035 g/m2 by emulsification-dispersion.
• condition A white imagewise exposure
• condition B condition B
• the difference in the red filter sensitivity of condition B samples and condition A samples are tabulated in Table 1 as changes in sensitivity after standing and the relative sensitivities of cyan and magenta images for condition A are also tabulated in Table 1.
• MTF values of magenta color images at 40 cycles/mm were measured by first uniformaly exposing the samples in an exposure amount of 0.02 CMS using a red filter, then exposing the samples to a MTF-measuring pattern using white light and developing them. Measurement of MTF was conducted according to Mees, The Theory of the Photographic Process , (3rd ed. Mcmillan Co.).
• Sample 201 was prepared in the same manner as sample 125 except for providing the following DC (dye conpensator) layer between the 7th and the 8th layers.
• DC layer (interlayer) Gelatin 0.80 EX-6 0.10 A-2 0.03 HBS-1 0.20
• Sample 208 was prepared in the same manner as sample 201 except for changing coupler EX-6 in the 7th, 8th, and DC layers to 0.8 time mol of coupler M-7 in accordance with the present invention and changing the amounts of HBS-1 and gelatin to 0.6 time and 0.7 time, respectively.
• Sample 215 was prepared in the same manner except for changing coupler EX-6 to 0.5 time mol of coupler M-16 in accordance with the present invention and changing the amounts of HBS-1 and gelatin to 0.5 time and 0.6 time, respectively.
• Sample 222 was prepared in the same manner except for changing coupler EX-6 to 0.4 time of coupler M-­3 in accordance with the present invention and changing the amounts of HBS-1 and gelatin to 0.3 time and 0.5 time respectively.
• Samples shown in Table 2 were prepared by replacing Compound A-2 added to the DC layer of samples 201, 208, 215, and 222 to equimolar amounts of A-3, A-4, compound (11), compound (15), compound (17), and compound (30) of the present invention, respectively.
• samples were exposed through a step wedge for measuring RMS graininess and subjected to the same color development to determine RMS values of the magenta images using an aperture 48 ⁇ m in diameter.
• the MTF values of the magenta images were also measured by exposure with white light. Processing Color development 3'15" Bleaching 1' Bleach-fixing 3'15" Washing with water (1) 40" Washing with water (2) 1' Stabilizing 40” Drying (50°C) 1'15"
• washing (1) and washing (2) were conducted by counter current washing from (2) to (1).
• Formulations of the respective processing solutions are shown below. Additionally, replenishing amounts of the processing solutions were as follows: Replenishing amount of the color developer was 1,200 ml per m2 of color light-sensitive material, and that of other solutions was 800 ml per m2 of color light-­sensitive material. The amount of the processing solution carried over from the bleach-fixing to the washing step was 50 ml per m2 of color light-sensitive material.
• City water containing 32 mg/liter or calcium ions and 7.3 mg/liter of magnesium ions was passed through a column filled with a H-type strongly acidic cation exchange resin and a OH-type strongly basic anion exchange resin to reduce the calcium ion level and the magnesium ion level to 1.2 mg/liter and 0.4 mg/liter, respectively.
• To the thus-processed water was added 20 mg/liter of sodium dichloroisocyanurate.
• Drying temperature was 50°C.

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• 1986
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