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
  • G03C7/305—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers
  • G03C7/30511—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers characterised by the releasing group
  • G03C7/30517—2-equivalent couplers, i.e. with a substitution on the coupling site being compulsory with the exception of halogen-substitution
  • G03C7/30523—Phenols or naphtols couplers

Definitions

• This invention relates to a silver halide color photographic material, and more particularly to a silver halide color photographic material which forms a cyan dye image whose density is not reduced even when processed with a bleaching bath or bleach-fix bath has been fatiqued or otherwise has a weak oxidizing capacity, and also forms an image excellent in sharpness.
• an aromatic primary amine color developing agent oxidized with an exposed silver halide can be reacted with a coupler to produce a dye, such as indophenol dyes, indoaniline dyes, indamine dyes, azomethine dyes, phenoxazine dyes, phenadine dyes, or the like, to form a dye image.
• a dye such as indophenol dyes, indoaniline dyes, indamine dyes, azomethine dyes, phenoxazine dyes, phenadine dyes, or the like
• phenolic couplers or naphthoic couplers known as cyan dye image forming couplers have been noted to have a disadvantage that the dye image produced therefrom has low fastness to heat or light, or undergoes density reduction when processed with a bleaching bath or bleach-fix bath having weak oxidizing capacity or a fatigued bleaching bath or bleach-fix bath.
• phenolic cyan couplers having a phenylureido group at the 2-position and a carbonamido group at the 5-position have been disclosed, e.g., in Japanese Patent Application (OPI) Nos.
• Japanese Patent Application (OPI) No. 11452/81 discloses a light-sensitive material containing a high-­boiling point organic solvent in an amount of from 0.01 to 0.3% by weight based on a total amount of 5-­pyrazolone magenta couplers.
• this technique aims at improvement on resistance to formaldehyde, and is, hence, entirely different from the present invention, from the standpoint of developed hue and effects.
• One object of this invention is to provide a silver halide color photographic light-sensitive material which does not undergo reduction in cyan color density even when processed with a bleaching bath or bleach-fix bath having been fatigued or having a weak oxidizing capacity.
• Another object of this invention is to provide a silver halide color photographic light-sensitive material having excellent dye image preservability.
• a further object of this invention is to provide a silver halide color photographic material having excellent sharpness.
• a silver halide color photographic material comprising a support having provided thereon at least one silver halide emulsion layer containing a cyan coupler, at least one silver halide emulsion layer containing a magenta coupler, and at least one silver halide emulsion layer containing a yellow coupler, wherein said cyan coupler-containing emulsion layer contains at least one cyan coupler represented by formula (I) shown below and a high-­boiling point organic solvent in an amount of not more than 30% by weight based on the total amount of said cyan coupler(s).
• Formula (I) is represented by wherein R1 represents -CONR5R6, -NHCOR5, -NHCOOR7, -NHSO2R7, -NHCONR5R6 or -NHSO2NR5R6, wherein R5 and R6 (which may be the same or different) each represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group, or R5 and R6 are taken together to form a nitrogen-containing heterocyclic ring, and R7 represents an aliphatic group, an aromatic group or a heterocyclic group; R2 represents a group capable of substituting for a hydrogen atom of a naphthalene ring, or a plurality of R2 (which may be the same or different) groups together form a ring; m represents 0 or an integer of from 1 to 3; R3 represents a monovalent organic group; and X represents a hydrogen atom or a group releasable upon coupling with an oxidation product of an aromatic primary
• R6 and R7 in groups represent­ ing R1 each preferably represents an aliphatic group having from 1 to 30 carbon atoms, an aromatic group having from 6 to 30 carbon atoms, and a heterocyclic group having from 2 to 30 carbon atoms.
• Typical examples of the group (or atom, hereinafter the same) capable of substituting for a hydrogen atom of a naphthalene ring as represented by R2 include a halogen atom, a hydroxyl group, an amino group, a carboxyl group, a sulfonic acid group, a cyano group, an aliphatic group, an aromatic group, a heterocyclic group, a carbonamido group, a sulfon­amido group, a carbamoyl group, a sulfamoyl group, a ureido group, an acyl group, an acyloxy group, an aliphatic oxy group, an aromatic oxy group, an aliphatic thio group, an aromatic thio group, an aliphatic sulfonyl group, an aromatic sulfonyl group, a sulfamoyl­amino group, a nitro group, an imido group,
• the monovalent organic group as represented by R3 preferably includes a group represented by formula (II) R8(Y) n - (II) wherein Y represents NH, CO or SO2; n represents 0 or 1; and R8 represents a hydrogen atom, an aliphatic group having from 1 to 30 carbon atoms, an aromatic group having from 6 to 30 carbon atoms, a heterocyclic group having from 2 to 30 carbon atoms, wherein R9, R10, and R11 each has the same meaning as R5, R6, and R7 as above defined, and R9 and R10 may be taken together to form a nitrogen-containing heterocyclic ring.
• formula (II) R8(Y) n - (II) wherein Y represents NH, CO or SO2; n represents 0 or 1; and R8 represents a hydrogen atom, an aliphatic group having from 1 to 30 carbon atoms, an aromatic group having from 6 to 30 carbon atoms, a heterocyclic group having from 2 to 30
• Examples of the nitrogen-containing hetero­cyclic ring formed by -NR5R6 or -NR9R10 include a morpholine ring, a piperidine ring, a pyrrolidine ring, etc.
• Typical examples of the group (or atom, herein­after the same) releasable upon coupling as represented by X include a halogen atom, an aromatic azo group having from 6 to 30 carbon atoms, a hetero­cyclic group having from 1 to 30 carbon atoms containing a nitrogen atom at which to bond to the coupling position of the coupler (e.g., succinimido group, a phthalimido group, a hydantoinyl group a pyrazolyl group, a 2-benzotriazolyl group, etc.), etc., wherein R12 represents an aliphatic group having from 1 to 30 carbon atoms, an aromatic group having from 6 to 30 carbon atoms or a heterocyclic group having from 2 to 30 carbon atoms.
• a halogen atom an aromatic azo group having from 6 to 30 carbon atoms
• a hetero­cyclic group having from 1 to 30 carbon atoms containing a nitrogen atom at which to bond to the
• aliphatic group as used herein includes saturated or unsaturated, substituted or un­substituted, and straight or branched chain or cyclic groups. Typical examples of the aliphatic group are a methyl group, an ethyl group, a butyl group, a cyclo­hexyl group, an allyl group, a propargyl group, a methoxyethyl group, an n-decyl group, an n-dodecyl group, an n-hexadecyl group, a trifluoromethyl group, a heptafluoropropyl group, a dodecyloxypropyl group, a 2,4-di-t-amylphenoxypropyl group, a 2,4-di-t-amyl­phenoxybutyl group, etc.
• aromatic group as used herein includes substituted or unsubstituted groups. Typical examples of the aromatic group are a phenyl group, a tolyl group, a 2-tetradecyloxyphenyl group, a penta­fluorophenyl group, a 2-chloro-5-dodecyloxycarbonyl­phenyl group, a 4-chlorophenyl group, a 4-cyanophenyl group, a 4-hydroxyphenyl group, etc.
• heterocyclic group as used herein includes substituted or unsubstituted groups. Typical examples of the heterocyclic groups are a 2-pyridyl group, a 4-pyridyl group, a 2-furyl group, a 4-thienyl group, a quinolinyl group, etc.
• R1 preferably represents -CONR5R6.
• -CONR5R6 include a carbamoyl group, an ethylcarbamoyl group, a morpholinocarbonyl group, a dodecylcarbamoyl group, a hexadecylcarbamoyl group, a decyloxypropylcarbamoyl group, a dodecyloxypropylcarbamoyl group, a 2,4-di-t-amylphenoxypropylcarbamoyl group, a 2,4-di-t-­amylphenoxybutylcarbamoyl group, etc.
• R2 preferably represents a halogen atom, an aliphatic group, a carbonamido group, a sulfonamido group, etc. More preferably m in (R) m is zero.
• R3 preferably represents the group of formula (II) wherein n is 0, and R8 represnets -COR9 (e.g., a formyl group, an acetyl group, a trifluoroacetyl group, a chloroacetyl group, a benzoyl group, a penta­fluorobenzoyl group, a p-chlorobenzoyl group, etc.), -COOR11 (e.g., a methoxycarbonyl group, an ethoxy­carbonyl group, a butoxycarbonyl group, a decyloxy­carbonyl group, a methoxyethoxycarbonyl group, a phenoxycarbonyl group, etc.), -SO2R11 (e.g., a methane­ sulfonyl group, an ethanesulfonyl group, a butanesulfonyl group, a hexadecan
• X preferably represents a hydrogen atom, a chlorine atom, an aliphatic oxy group (e.g., a 2-hydroxyethoxy group, a 2-chloroethoxy group, a carboxymethyloxy group, a 1-carboxyethoxy group, a 2-methanesulfonylethoxy group, a 3-carboxypropyloxy group, a 2-methoxyethoxycarbamoylmethyloxy group, a 1-carboxytridecyl group, a 2-(1-carboxytridecylthio)­ethyloxy group, a 2-carboxymethylthioethyloxy group, a 2-methanesulfonamidoethyloxy group, etc.), an aromatic oxy group (e.g., a 4-acetamidophenoxy group, a 2-acet­amidophenoxy group, a 4-(3-carboxypropaneamido)phenoxy group, etc.) or
• the cyan coupler according to the present invention includes a polymer inclusive of a dimer wherein two or more monomer units derived from the compound of formula (I) are connected at any of R1, R2, R3, and X via a divalent or higher valent group.
• each of the above-illustrated substituents may have a total carbon atom number out of the range respectively recited.
• such a polymeric coupler typically includes a homo- or co­polymer of an addition polymerizable ethylenically unsaturated compound having a cyan dye forming coupler residue (cyan forming monomer).
• a polymer comprises one or more repeating units represented by formula (III) shown below, and, if desired, one or more non-color-forming ethylenically unsaturated monomers as copolymerizable units.
• Formula (III) is represented by wherein R represents a hydrogen atom, an alkyl group having from 1 to 4 carbon atoms or a chlorine atom; A represents -CONH-, -COO- or a substituted or unsubstituted phenylene group; B represents a sub­stituted or unsubstituted alkylene, phenylene or aralkylene group; L represents -CONR ⁇ -, -NR ⁇ CONR ⁇ -, -NR ⁇ COO-, -NR ⁇ CO-, -OCONR ⁇ -, -NR ⁇ -, -COO-, -OCO-, -CO-, -O-, -SO2-, -NR ⁇ SO2- or -SO2NR ⁇ , wherein R ⁇ represents a hydrogen atom or a substituted or unsubstituted alkyl or aryl group; a, b, and c each represents 0 or 1; and Q represents a cyan coupler residual group derived from the compound represented
• the polymeric coupler preferably includes a copolymer comprising the cyan forming monomer providing the repeating unit of formula (III) and the non-color-forming ethylenically unsaturated comonomers which do not couple with an oxidation product of an aromatic primary amine developing agent.
• acrylic acid ⁇ -chloro­acrylic acid, ⁇ -alacrylic acid (e.g., methacrylic acid), esters or amides of these acrylic acids (e.g., acrylamide, methacrylamide, n-butylacrylamide, t-butylacrylamide, diacetonacrylamide, 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, ⁇ , ⁇ -hydroxymethacrylate, etc.), vinyl esters (e.g., vinyl acetate, vinyl propionate, vinyl laurate, etc.), acrylonitrile,
• acrylic esters meth­acrylic esters, and maleic esters are preferred.
• These non-color-forming ethylenically unsaturated monomers may be used either individually or in combinations of two or more thereof. For example, a combination of methyl acrylate and butyl acrylate, a combination of butyl acrylate and styrene, a combination of butyl methacrylate and methacrylic acid, a combination of methyl acrylate and diacetonacrylamide, etc. can be employed.
• the kind of the ethylenically unsaturated monomers to be copolymerized with vinyl monomers corres­ponding to the repeating unit of formula (III) can be selected appropriately so as to exert favorable influences upon physical and/or chemical properties of the resulting copolymers, such as solubility, com­patibility with binders for photographic colloidal compositions, e.g., gelatin, flexibility, heat stability, and the like.
• the polymeric coupler which can be used in the present invention can be prepared by polymerizing the vinyl monomer providing the repeating unit of formula (III), dissolving the resulting oleophilic polymer in an organic solvent, and dispersing the organic solution in a gelatin aqueous solution to form a latex.
• the process disclosed in U.S. Patent 3,451,820 may be applied to a dispersion of the oleophilic polymer in a gelatin aqueous solution.
• the polymeric coupler may also be prepared by direct emulsion polymerization in accordance with the process as disclosed in U.S. Patents 4,080,211 and 3,370,952.
• the couplers represented by formula (I) can be synthesized easily in accordance with the process described in European Patent 161626A.
• the high-boiling point organic solvents which can be used in the present invention are those having a boiling point of 175°C or higher at normal pressure (760 mmHg).
• Examples of the high-boiling point organic solvents which can be used in combination with the couplers of formula (I) include phosphoric esters, e.g., tri­phenyl phosphate, tricresyl phosphate, octyldiphenyl phosphate, tri-2-ethylhexyl phosphate, tri-n-hexyl phosphate, tri-iso-nonyl phosphate, tricyclohexyl phosphate, tributoxyethyl phosphate, tri-2-chloroethyl phosphate, etc.; benzoic esters, e.g., 2-ethylhexyl benzoate, 2-ethylhexyl 2,4-dichlorobenzoate, etc.; fatty acid esters, e.g., di-2-ethylhexyl succinate, 2-hexyldecyl tetradecanoate, tributyl citrate,
• the amount of the high-boiling point organic solvent to be used in this invention should not exceed 0.3 g per gram of the coupler of formula (I) (i.e., it should not exceed 30 wt%). If it exceeds 0.3 g/g-coupler, sharpness is conspicuously deterio­rated.
• a preferred amount of the high-boiling point solvent is 0.15 g or less, more preferably 0.05 g or less, and most preferivelyably 0.01 g or less, per gram of the coupler.
• the high-boiling point organic solvent may not be used at all.
• the coupler is emulsified in the hydrophilic colloid by using a low-­boiling point organic solvent (having a boiling point of from about 30°C to about 160°C, such as 2-ethoxyethyl acetate, N,N-dimethyl­formamide, etc.)
• a low-­boiling point organic solvent having a boiling point of from about 30°C to about 160°C, such as 2-ethoxyethyl acetate, N,N-dimethyl­formamide, etc.
• the amount of the cyan coupler represented by formula (I) usually ranges from 1.0 ⁇ 10 ⁇ 5 to 3.0 ⁇ 10 ⁇ 3 mol/m2, and preferably from 5.0 ⁇ 10 ⁇ 5 to 1.5 ⁇ 10 ⁇ 3 mol/m2.
• the present invention is preferably applied to layers other than the layer having the highest sensitivity.
• magenta couplers which can be used in the present invention are preferably polymeric magenta couplers, and more preferably those obtained from a monomer represented by formula (IV) wherein R21 represents a hydrogen atom, an alkyl group having from 1 to 4 carbon atoms or a chlorine atom; D represents -COO-, -CONR22- or a substituted or un­substituted phenyl group; E represents a substituted or unsubstituted alkylene, phenylene or aralkylene group having from 1 to 10 carbon atoms; F represents -CONR22-, -NR22CONR22-, -NR22COO-, -NR22CO-, -OCONR22-, -NR22-, -COO-, -OCO-, -CO-, -O-, -S-, -SO2-, -NR22SO2- ­or -SO2NR22-, wherein R22 represents a hydrogen atom or
• Formula (V) is represented by wherein Ar represents an alkyl group, an aryl group, and a heterocyclic group; R23 represents a substituted or unsubstituted anilino group, a substituted or unsubstituted acylamino group (e.g., an alkylcarbonamido group, a phenylcarbonamido group, an alkoxycarbonamido group, a phenyloxycarbonaido group, etc.), a substituted or unsubstituted ureido group (e.g., an alkylureido group, a phenylureido group, etc.) or a substituted or unsubstituted sulfonamido group; and Z represents a hydrogen atom, a halogen atom (e.g., a chlorine atom, a bromine atom, etc.), a coupling releasable group bonded via an oxygen atom (e.g., an
• 2,132,783 e.g., a benzenesulfonamido group, an N-ethyltoluenesulfonamido group, a heptafluorobutaneamido group, a 2,3,4,5,6-­pentafluorobenzamido group, an octanesulfonamido group, a p-cyanophenylureido group, an N,N-diethyl­sulfamoylamino group, a 1-piperidyl group, a 5,5-dimethyl-2,4-dioxo-3-oxazolidinyl group, a 1-­benzyl-5-ethoxy-3-hydantoinyl group, a 2-oxo-1,2-di­hydro-1-pyridinyl group, an imidazolyl group, a pyrazolyl group, a 3,5-diethyl-1,2,4-triazol-1
• the coupler residual group T of formula (V) is bonded to (D) (E) (F) at any of Ar, X, and R23.
• the group as represented by Ar includes a substituted or unsubstituted alkyl group (the substituent includes a halogen atom, a cyano group, a benzyl group, etc.), a substituted or unsubstituted heterocyclic group (e.g., a 4-pyridyl group, a 2-thia­zoyl group, etc.), and a substituted or unsubstituted aryl group.
• the substituent for the heterocyclic group or aryl group includes 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 dimethylcarbamoyl group, etc.), an arylcarbamoyl group (e.g.
• these groups When two or more of these groups substitute the heterocyclic or aryl group, they may be the same or different. Preferred among these substituents are a halogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, and a cyano group.
• the substituent for the group as represented by R23 includes a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, etc.), a straight or branched chain alkyl group (e.g., a methyl group, a t-butyl group, an octyl group, a tetradecyl group, etc.), an alkoxy group (e.g., a methoxy group, an ethoxy group, a 2-ethylhexyloxy group, a tetradecyloxy group, etc.), an acylamino group (e.g., an acetamido group, a benzamido group, a butanamido group, an octanamido group, a tetradecanamido group, an ⁇ -(2,4-di-t-amyl­phenoxy)acetamido group, an ⁇ -
• Z preferably represents a coupling releasable group bonded at a nitrogen atom, and more preferably a pyrazolyl group.
• the alkylene group as represented by E in formula (IV) may have either a straight chain or a branched chain.
• Examples of the alkylene group are a methylene group, a methylmethylene group, a dimethyl­methylene group, a dimethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a decylmethylene group, etc.
• Examples of the aralkylene group as represented by E are a benzylidene group, and the phenylene group as represented by E are a p-phenylene group, an m-phenylene group, a methylphenylene group, etc.
• the substituents for these groups as E include an aryl group (e.g., a phenyl group, etc.), a nitro group, a hydroxyl group, a cyano group, a sulfo group, an alkoxy group (e.g., a methoxy group, etc.), an aryl­oxy group (e.g., a phenoxy group, etc.), an acyloxy group (e.g., an acetoxy group, etc.), an acylamino group (e.g., an acetylamino group, etc.), a sulfonamido group (e.g., a methanesulfonamido group, etc.), a sulfamoyl group (e.g., a methylsulfamoyl group, etc.), a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom,
• the polymeric magenta coupler which can be used in the present invention includes not only a homopolymer or copolymer of the monomer represented by formula (IV), but also a copolymer obtained from the monomer of formula (IV) and non-color-forming ethylenically unsaturated monomers which do not couple with an oxidation product of an aromatic primary amine developing agent.
• non-color-forming ethylenically unsaturated monomer to be copolymerized with the monomer of formula (IV) are acrylic esters, e.g., methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, acetoxyethyl acrylate, phenyl acrylate, 2-­methoxy acrylate, 2-ethoxy acrylate, 2-(2-­methoxyethoxy)ethyl acrylate, etc.; methacrylic esters, e.g., methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, t-butyl methacrylate,
• Examples of other comonomers to be copolymerized with the monomer of formula (IV) include allyl compounds (e.g., allyl acetate, etc.), vinyl ketones (e.g., methyl vinyl ketone, etc.), vinyl hetero­cyclic compounds (e.g., vinylpyridine, etc.), glycidyl esters (e.g., glycidyl acrylate, etc.), unsaturated nitriles (e.g., acrylonitrile, etc.), acrylic acid, methacrylic acid, itaconic acid, maleic acid, itaconic acid monoalkyl esters (e.g., monomethyl itaconate, etc.), maleic acid monoalkyl esters (e.g., monomethyl maleate, etc.), citraconic acid, vinylsulfonic acid, acryloyloxyalkylsulfonic acids (e.g., acryloyloxymethyl­sulfonic acid, etc.), acryla
• comonomers are acrylic esters, methacrylic esters, styrenes, maleic esters, acrylamides, and methacrylamides. These comonomers may be used either individually or in combinations of two or more thereof. For example, a combination of n-butyl acrylate and styrene and a combination of n-butyl acrylate and butylstyrene, t-butylmethacrylamide and n-butyl acrylate can be employed.
• polymeric magenta couplers usually contain the monomer unit derived from the compound of formula (IV) in a proportion of from 5 to 80% by weight, and preferably from 30 to 70% by weight in view of color reproducibility, color developability, and stability.
• These polymeric magenta couplers usually have an equivalent molecular weight (grams of polymer containing 1 mol of a monomer coupler) of about 250 to 4,000, though not limiting.
• the polymeric couplers according to the present invention are added to a silver halide emulsion layer or layers adjacent thereto.
• the amount of the polymeric magenta coupler to be used ranges from 0.005 to 0.5 mol, and preferably from 0.01 to 0.10 mol, per mol of silver.
• the amount to be used ranges from 0.01 to 1.0 g, and preferably from 0.1 to 0.5 g, per m2.
• the polymeric magenta couplers can be prepared in the same manner as described for polymeric cyan couplers using the processes of U.S. Patents 3,451,820, 4,080,211, and 3,370,952, etc.
• the above-described polymeric magenta couplers can be synthesized by using polymerization initiators and solvents disclosed in Japanese Patent Application (OPI) Nos. 5543/81, 94752/82, 176038/82, 204038/82, 28745/83, 10738/83, 42044/83, and 145944/83.
• the polymerization temperature should be determined in connection with the desired molecular weight of the resulting polymer, the kind of the polymerization initiator to be used, or like factors can be selected from a wide range of from 0°C or less up to 100°C or more, and usually of from 30°C to 100°C.
• polymeric magenta couplers which can be used in the present invention are shown below.
• Silver halide which can be used in the photo­graphic emulsion layer of the photographic material of the present invention may be any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride.
• Preferred are silver iodobromide and silver iodochlorobromide having a silver iodide content of not more than about 30 mol%, and more preferred is silver iodobromide having a silver iodide content of from about 2 to about 25 mol%.
• the silver halide grains in the photographic emulsion may have a regular crystal form, such as cubic, octahedral and tetradecahedral forms, an irregular crystal form, such as a spherical form, a crystal form having a defect, such as a twin, or a composite crystal form thereof.
• the silver halide may be fine grains having a grain size of about 0.1 ⁇ m or smaller or giant grains having a projected area diameter reaching about 10 ⁇ m.
• the silver halide emulsion may be a mono-dispersion having narrow size distribution or a poly-dispersion having broad size distribution.
• the silver halide emulsions to be used can be prepared by known processes as disclosed, e.g., in Research Disclosure , No. 17643, pp.22-23, "I. Emul­sion Preparation and Types" (Dec., 1978), ibid , No. 18716, p.648 (Nov., 1979), 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.
• the emulsion can be prepared by any of the acid process, the neutral process, the ammonia process, etc.
• the reaction between a soluble silver salt and a soluble halogen salt can be carried out by any of a single jet process, a double jet process, a combination thereof, and the like.
• a so-called reverse mixing process in which grains are formed in the presence of excess silver ions may be used.
• a so-called controlled double jet process in which a pAg value of a liquid phase in which silver halide grains are formed is maintained constant, may also be used.
• a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained. Two or more silver halide emulsions separate­ly prepared may be used as a mixture.
• the silver halide emulsion comprising grains having a regular crystal form can be prepared by controlling pAg and pH values during grain formation.
• the monodisperse emulsion as above referred to typically includes those containing silver halide grains having a mean grain size of about 0.1 ⁇ m or greater, and particularly of from about 0.25 to 2 ⁇ m, in which at least about 95% by weight or number of the total grains fall within a size range of 40%, and particularly 20%, of the mean grain size.
• Such monodisperse emulsions can be prepared by the processes described in U.S. Patents 3,574,628 and 3,655,394, and British Patent 1,413,748.
• the monodisperse emulsions described in Japanese Patent Application (OPI) Nos. 8600/73, 39027/76, 83097/76, 137133/78, 48521/79, 99419/79, 37635/83, and 49938/83, etc. can also be used to advantage in the present invention.
• Plate-like (tabular) grains having an aspect ratio of about 5 or more (i.e., 5/1 or more) can also be used.
• Such plate-­like grains can be prepared easily by the processes described in Gutoff, Photographic 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, British Patent 2,112,157, etc.
• Use of the plate-like grains brings about improvements on efficiency of color sensitization by sensitizing dyes, graininess, sharpness, and the like, as suggested in U.S. Patent 4,434,226.
• the individual silver halide crystals may have either a homogeneous structure or a heterogeneous structure, such as a core-shell structure or a layered structure differing in halogen composition.
• emulsion grains are disclosed in British Patent 1,027,146, U.S. Patents 3,505,068 and 4,444,877, Japanese Patent Application No. 248469/B3, etc. Further, they may have a heterogeneous structure in which a silver halide grain having a different halogen composition or a compound other than silver halides, e.g., silver thiocyanate, lead oxide, etc., is fused by epitaxy.
• emulsion grains are disclosed in U.S.
• a mixture of silver halide grains having various crystal forms can also be employed.
• the emulsion to be used in the present invention is usually subjected to physical ripening, chemical ripening and spectral sensitization.
• Additives to be used in these steps and other photographically useful additives which can be used in the present invention are described in Research Disclosure (RD), No. l7643 (Dec. l978) and ibid , No. l87l6 (Nov. l979) as tabulated below.
• Yellow couplers to be used typically include hydrophobic acylacetamide couplers having a ballast group, whose specific examples are given in U.S. Patents 2,407,210, 2,875,057, and 3,265,506.
• 2-equivalent yellow couplers are preferred.
• Typical examples of such couplers are those of oxygen-­release type as described in U.S. Patents 3,408,194, 3,447,928, 3,933,501, and 4,022,620; and those of nitrogen-release type as described in Japanese Patent Publication No. 10739/83, U.S. Patents 4,401,752 and 4,326,024, Research Disclosure , No.
• ⁇ -pivaloylacetanilide couplers are excellent in color fastness, and particularly fast­ ness to light, and ⁇ -benzoylacetanilide couplers provide high color densities.
• the magenta couplers which can be used in the present invention include indazolone or cyanoacetyl couplers, and preferably 5-pyrazolone or pyrazoloazole couplers which have a ballast group and are thereby hydrophobic.
• the 5-pyrazolone couplers preferably have an arylamino group or an acylamino group at the 3-position from the standpoint of hue and density of the developed color. Typical examples of such couplers are described, e.g., in U.S. Patents 2,311,082, 2,343,703, 2,600,788, 2,908,573, 3,062,653, 3,152,896, and 3,936,015.
• Preferred releasable groups for 2-equivalent 5-pyrazolone couplers are nitrogen atom-­release type groups as described in U.S. Patent 4,310,619 and arylthio groups as described in U.S. Patent 4,351,897.
• 5-Pyrazolone couplers having the ballast group described in European Patent 73,636 provide high color densities.
• the pyrazoloazole couplers include pyrazolobenzimidazoles described in U.S. Patent 3,061,432, and preferably pyrazolo[5,1-c]­[1,2,4]triazoles described in U.S. Patent 3,725,067, pyrazolotetrazoles described in Research Disclosure , No.
• Cyan couplers which can be used in the present invention include hydrophobic and anti-diffusible naphthoic and phenolic couplers. Typical examples are naphthol couplers described in U.S. Patent 2,474,293, and preferably 2-equivalent naphthol couplers of oxygen-­release type described in U.S. Patents 4,052,212, 4,146,396, 4,228,233, and 4,296,200. Examples of the phenolic couplers are described in U.S. Patents 2,369,929, 2,801,171, 2,772,162, and 2,895,826.
• Cyan couplers which form cyan dyes fast to moisture and heat are advantageously used in the present invention.
• Typical examples of such cyan couplers include phenolic couplers having an alkyl group having at least 2 carbon atoms at the m-position as described in U.S. Patent 3,772,002; 2,5-diacylamino-substituted phenol couplers as described in U.S. Patents 2,772,162, 3,758,308, 4,126,396, 4,334,011, and 4,327,173, West German Patent Publication No.
• a colored coupler in combination for masking in color light-senisitive materials for photogrpahing.
• Typical examples of the colored couplers are yellow-colored magenta couplers described in U.S. Patent 4,163,670 and Japanese Patent Publication No. 39413/82 and magenta-colored cyan couplers described in U.S. Patents 4,004,929 and 4,138,258 and British Patent 1,146,368.
• Other examples of colored couplers are described in Research Disclosure , No. 17643, VII-G (Dec. 1978).
• Graininess can be improved by using a coupler which forms a dye having moderate diffusibility.
• a coupler which forms a dye having moderate diffusibility. Examples of such a coupler are described in U.S. Patent 4,366,237 and British Patent 2,125,570 for magenta couplers; and in European Patent 96,570 and West German Patent Publication No. 3,234,533 for yellow, magenta, and cyan couplers.
• the dye forming couplers and the above-described special couplers may be in the form of a polymer including a dimer.
• Typical examples of polymerized dye forming couplers are described in U.S. Patents 3,451,820 and 4,080,211.
• Typical examples of polymerized magenta couplers are described in British Patent 2,102,173 and U.S. Patent 4,367,282.
• Couplers capable of releasing a photographical­ly useful residue upon coupling can also be used in this invention with advantage.
• Useful examples of DIR couplers which release a developing inhibitor are described in Research Disclosure , No.l7643, VII-F (Dec. l978).
• DIR (development inhibitor releasing) couplers which are preferably combined with the present invention include those which are inactivated in a developer as described in Japanese Patent Application (OPI) No. 151944/82; timing type DIR couplers as described in U.S. Patent 4,248,962 and Japanese Patent Application (OPI) No. 154234/82; and reactive type DIR couplers as described in Japanese Patent Application (OPI) No. 39653/84.
• Particularly preferred are developer-inactivated type DIR couplers described in Japanese Patent Application (OPI) Nos. 151944/82 and 217932/83 and Japanese Patent Application Nos. 75474/84, 82214/84, and 90438/84; and reactive type DIR couplers described in Japanese Patent Application No. 39653/84.
• the light-sensitive materials of the present invention can also use couplers which imagewise release a nucleating agent or a development accelerator or a precursor thereof at the time of development.
• couplers which imagewise release a nucleating agent or a development accelerator or a precursor thereof at the time of development.
• couplers are described in British Patents 2,097,140 and 2,131,188. Couplers capable of releasing a nucleating agent having adsorp­tivity onto silver halide, such as those described in Japanese Patent Application (OPI) Nos. 157638/84 and 170840/84, are particularly preferred.
• the color photographic material in accordance with the present invention can be subjected to development processing by known methods as described, e.g., in Research Disclosure , No. 17643, pp.28-29 (Dec. l978) ibid , No. l87l6, p. 65l, left to right columns (Nov.l979).
• Color developing solutions to be used for development processing preferably include alkaline aqueous solutions containing, as a main component, an aromatic primary amine developing agent.
• Usable color developing agents include aminophenol compounds, and preferably p-phenylenediamine compounds. Typical examples of the latter are 3-methyl-4-amino-N,N-di­ ethylaniline, 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 or p-toluene­sulfonates thereof.
• These diamines are more stable and thereby preferred in the form of a salt rather than in a free form.
• the color developing solutions generally contain pH buffers, such as carbonates, borates or phosphates of alkali metals, and developing inhibitors or antifoggants, such as bromides, iodides, benzimida­zoles, benzothiazoles, mercapto compounds, etc.
• pH buffers such as carbonates, borates or phosphates of alkali metals
• inhibitors or antifoggants such as bromides, iodides, benzimida­zoles, benzothiazoles, mercapto compounds, etc.
• the color developing solutions may further contain preservatives, e.g., hydroxylamines, sulfites, etc.; organic solvents, e.g., triethanolamine, diethylene glycol, etc.; development accelerators, e.g., benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines, etc.; competing couplers; nucleating agents, e.g., sodium boron hydride, etc.; auxiliary developing agents, e.g., 1-phenyl-3-pyrazoli­done, etc.; tackifiers; various chelating agents, e.g., aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, phosphonocarboxylic acids, etc.; antioxidants, e.g., those described in West German Patent Publication No. 2,622,950; and the like.
• preservatives e.g., hydroxylamines, sulfites, etc
• Black-and-white developing solutions 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).
• dihydroxy­benzenes e.g., hydroquinone
• 3-pyrazolidones e.g., 1-phenyl-3-pyrazolidone
• aminophenols e.g., N-­methyl-p-aminophenol
• bleaching The photographic emulsion layers after color development are usually subjected to bleaching.
• Bleach­ing may be effected simultaneously with fixation, or these two steps may be carried out separately.
• bleaching may be followed by bleach-fixation (blix).
• Bleaching agents to be used in bleaching or blix include compounds of poly­valent metals, e.g., iron (III), cobalt (III), chromium (VI), copper (II), etc., peracids, quinones, nitroso compounds, and the like.
• bleaching agents are ferricyanides; bichromates; organic complex salts of iron (III) or cobalt (III), such as complex salts with aminopolycarboxylic acids, e.g., ethylene­diaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, 1,3-diamino-2-propanol­tetraacetic acid, etc., or organic acids, e.g., citric acid, tartaric acid, malic acid, etc.; persulfates; manganates; nitrosophenol; and so on.
• aminopolycarboxylic acids e.g., ethylene­diaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, 1,3-diamino-2-propanol­tetraacetic acid, etc.
• organic acids e.g., citric acid, tartaric acid, malic acid
• (ethylenediaminetetraacetato)iron (III) salts are preferred in view of speeding up of processing and conservation of the environment.
• (ethylenediaminetetraacetato)iron (III) salts are useful in both of an independent bleaching bath and a bleach-fix monobath.
• the bleaching bath, bleach-fix bath or a pre-­bath thereof can contain, if desired, a bleaching accelerator.
• a bleaching accelerator examples include compounds having a mercapto group or a disulfide group as described in U.S. Patent 3,893,858, West German Patents 1,290,812 and 2,059,988, Japanese Patent Application (OPI) Nos. 32736/78, 57831/78, 37418/78, 65732/78, 72623/78, 95630/78, 95631/78, 104232/78, 124424/78, 141623/78 and 28426/78, Research Disclosure , No. 17129 (July 1978); thiazolidine derivatives as described in Japanese Patent Application (OPI) No.
• Fixing agents to be used for fixation include thiosulfates, thiocyanates, thioethers, thioureas, and a large amount of iodides, with thiosulfates being commonly employed. Sulfites, bisulfites or carbonyl­bisulfite addition compounds are suitably used as pre­servatives of the bleach-fix bath or fixing bath.
• washing and stabilizing solutions may contain various known compounds for the purpose of preventing precipitation or saving water.
• additives to be used for prevention of precipitation include water softeners, such as inorganic phosphoric acids, aminopolycarboxylic acids, organic aminopolyphosphonic acids, organic phosphoric acids, etc.; bactericides or fungicides; and metal salts, such as magnesium salts, aluminum salts and bismuth salts.
• Surface active agents and various hardeners can also be added for the purpose of reducing a drying load or preventing uneven drying.
• the compounds described in L.E. West, Photo. Sci. Eng. , Vol. 6, pp.344-359 (1965) may also be used. In parti­cular, addition of chelating agents and fungicides is effective.
• Washing is generally carried out by using two or more washing vessels arranged countercurrently, by which water saving can be effected.
• the washing step may be replaced by a multi-stage countercurrent stabilization step as described in Japanese Patent Application (OPI) No. 8543/82, in which 2 to 9 vessels arranged countercurrently are required.
• the stabilization baths to be used in this step contain various compounds for image stabilization in addition to the aforesaid additives.
• Such compounds include various buffers for film pH adjustment (e.g., to a pH of from 3 to 9) (e.g., borates, metaborates, borax, phosphonates, carbonates, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acids, di­carboxylic acids, polycarboxylic acids and combinations thereof) and aldehydes, e.g., formalin.
• buffers for film pH adjustment e.g., to a pH of from 3 to 9
• buffers for film pH adjustment e.g., to a pH of from 3 to 9
• buffers for film pH adjustment e.g., to a pH of from 3 to 9
• buffers for film pH adjustment e.g., to a pH of from 3 to 9
• aldehydes e.g., formalin.
• the stabilization bath may further contain other additives, such as chelating agents (e.g., inorganic phosphoric acids, aminopolycarboxylic acids, organic phosphoric acids, aminopolyphosphonic acids, phosphono­carboxylic acids, etc.), bactericides (e.g., benzoisothiazolinone, crizotin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, bactericides (e.g., benzoisothiazolinone, crizoazolinone, aric acid, etc.), bactericides (e.g., benzoisothiazolinone, crizhiazolone, 4-thiazolinebenz­imidazole, halogenated phenols, sulfanilamide, benzo­triazole, etc.), surface active agents, fluorescent brightening agents, hardeners, and the like. These compounds may be added in combinations of two or more thereof for the same or different purposes.
• ammonium salts it is preferable to add various ammonium salts to the stabilization bath as film pH adjusting agents after processing.
• ammonium salts are ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, ammonium thiosulfate, etc.
• the (washing-stabilization) step after fixation that is commonly adopted may be replaced by the aforesaid stabilization step and washing step (water saving processing).
• the magenta coupler used is 2-equivalent, formalin may be excluded from the stabilization bath.
• the time required for washing and stabilization varies depending on the type of the light-sensitive material processed and the conditions for processing, and usually ranges from 20 seconds to 10 minutes, and preferably from 20 seconds to 5 minutes.
• a color developing agent preferably in the form of its precursor, can be incorporated into the silver halide color photographic material according to the present invention.
• the precursors of the color developing agent suitable for incorporation include indoaniline compounds as described in U.S. Patent 3,342,597, Schiff base type compounds as in U.S. Patent 3,342,599, Research Disclosure , No. l4850 (Aug. l976) and ibid , No. l5l59 (Nov. l976), aldol compounds as in Research Disclosure , No. 13924, metal complexes as in U.S. Patent 3,719,492, urethane compounds as in Japanese Patent Application (OPI) No.
• the color light-sensitive materials of the present invention can further contain therein various 1-phenyl-­3-pyrazolidones. Typical examples thereof are described in Japanese Patent Application (OPI) Nos. 64339/81, 144547/82, 211147/82, 50532/83, 50536/83, 50533/83, 50534/83, 50535/83, and 115438/83, etc.
• Each of the above-described processing solutions is used at a temperature between 10°C and 50°C, and usually between 33°C and 38°C. It is possible to use higher temperatures to accelerate processing to thereby reduce the processing time or lower tempera­tures required to achieve improvements on image quality or stability of processing solutions.
• intensification may be carried out by using a cobalt or hydrogen peroxide intensifier, as described in West German Patent 2,226,770 or U.S. Patent 3,674,499.
• each of the processing baths may be provided with a heater, a temperature sensor, a liquid level sensor, a circulating pump, a filter, a floating lid, a squeegee, etc.
• Each of the above layers further contained Gelatin Hardener H-1 and a surface active agent.
• the coating composition for the 3rd layer was prepared as follows.
• Coupler I-13 60 g of Coupler I-13 and 3.4 g of Coupler C-4 under heating, and the solution was mixed with 1000 g of a 10 wt% aqueous solution of gelatin having dissolved therein 5.0 g of sodium dodecylbenzenesulfonate, and the mixture was dispersed in a domestic mixer for 10 minutes.
• Samples 102 to 110 were prepared in the same manner as for Sample 101, except that Couplers I-13 and C-4 as used in the 3rd and 4th layers were changed in kind and amount as shown in Table 1 below, and that the gelatin coverage was adjusted so that the film strength of the 3rd layer and that of the 4th layer were equal.
• Samples 101 to 110 were imagewise exposed to white light for sensitometry and then subjected to color development processing according to the following procedure at 38°C.
• the processed sample was determined for density through a red filter. Further, each of the samples was exposed to light through a pattern for MTF measurement and then subjected to the same color development processing to calculate an MTF value at a spatial frequency of 25 c/mm. The results obtained are shown in the Table.
• the processing solutions used in each processing step had the following formulations.
• Sample 201 was prepared in the same manner as for Sample 101 of Example 1, except for replacing Coupler C-4 in the 3rd and 4th layers with one-half the molar quantity of C-14, replacing Coupler C-5 in the 5th layer with two-third the molar quantity of Coupler I-14, and further replacing Coupler C-9 in the 9th layer with one-half the molar quantity of Coupler C-15.
• Samples 202 to 206 were prepared in the same manner as for Sample 201, except that the main coupler in the 3rd and 4th layers, Coupler I-13, was replaced with the equimolar amount of each of Couplers I-11, I-3, I-53, C-11, and C-13, respectively.
• Sample 207 was prepared in the same manner as for Sample 201, except for replacing the main coupler in the 7th and 8th layers, Coupler C-6, with double the molar amount of Coupler C-16 and using an additional amount of gelatin to make the film strength of both layers equal.
• Sample 208 was prepared in the same manner as for Sample 201, except that the main coupler of the 7th and 8th layers, Coupler C-6, was replaced with double the molar amount of Coupler C-9 and the amount of the organic solvent was doubled to make the color developability and preservability substantially equal to those of Sample 201.
• Example 1 Each of Samples 201 to 208 was exposed to light and development-processed in the same manner as described in Example 1.
• the processing of Example 1 is herein designated as Processing A.
• the sensitivity, gamma, and MTF values of the processed samples were determined.
• the cyan density of the processed samples on the point having been exposed at an exposure of 1 ⁇ 20 ⁇ 3 CMS was also measured. The results obtained are shown in Table 2 below.
• Process­ing B The bleaching solution used in Processing B was designed to be a model of a fatigued processing solution after use for processing a large quantity of light-sensitive materials.
• Sample 205 using the comparative coupler showed an extremely low color density so that the relative sensitivity, gamma, and MTF value were un­measurable.
• Sample 206 shows considerable reduction in cyan color density when processed with a fatigued bleaching solution.
• Samples 201 to 204 according to the present invention sufficiently satisfy these performance requirements, clearly demonstrating the effectiveness of the present invention. Further, it can be seen that Samples 207 or 208, in which a 4-equivalent polymeric magenta coupler (C-16) or a 4-equivalent magenta coupler (C-9) was used, respectively, in the 7th and 8th layers, shows a slight­ly reduced MTF value. In other words, the effects of the cyan couplers of the invention to improve sharpness can be ensured by using 2-equivalent magenta couplers in combination rather than 4-equivalent magenta couplers.
• C-16 4-equivalent polymeric magenta coupler
• C-9 4-equivalent magenta coupler

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• 1986
  • 1986-05-19 JP JP11403486A patent/JPS62269958A/ja active Pending
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