GB2098600A - Sulphonamido-containing 2,5- diacylaminophenol cyan couplers for cyan dye imaging - Google Patents

Sulphonamido-containing 2,5- diacylaminophenol cyan couplers for cyan dye imaging Download PDF

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GB2098600A
GB2098600A GB8207292A GB8207292A GB2098600A GB 2098600 A GB2098600 A GB 2098600A GB 8207292 A GB8207292 A GB 8207292A GB 8207292 A GB8207292 A GB 8207292A GB 2098600 A GB2098600 A GB 2098600A
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coupler
cyan
cyan coupler
silver halide
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D207/34—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D207/36—Oxygen or sulfur atoms
    • C07D207/40—2,5-Pyrrolidine-diones
    • C07D207/404—2,5-Pyrrolidine-diones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. succinimide
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    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/81—Amides; Imides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
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    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/81—Amides; Imides
    • C07D213/82—Amides; Imides in position 3
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
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    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D233/72—Two oxygen atoms, e.g. hydantoin
    • C07D233/76—Two oxygen atoms, e.g. hydantoin with substituted hydrocarbon radicals attached to the third ring carbon atom
    • C07D233/78—Radicals substituted by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D275/00—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings
    • C07D275/02—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings not condensed with other rings
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    • C07D279/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one sulfur atom as the only ring hetero atoms
    • C07D279/02—1,2-Thiazines; Hydrogenated 1,2-thiazines
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/22—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with hetero atoms directly attached to ring nitrogen atoms
    • C07D295/26—Sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • 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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/32—Colour coupling substances
    • G03C7/34—Couplers containing phenols
    • G03C7/346—Phenolic couplers

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Abstract

A method for forming a cyan dye image by imagewise processing of a silver halide color photographic photosensitive material in the presence of a 2,5-diacylaminophenol cyan coupler is disclosed. The acylamino group at 2- or 5-position of the phenolic nucleus of the cyan coupler has a substituent of the formula (I): <IMAGE> [wherein R1 is <IMAGE> R2 is an alkylene group; R3 is an alkyl group; R4 is a hydrogen atom, an alkyl group or an acyl group; X is a group that can be introduced in the benzene ring as a substituent; n is an integer of 1 to 3; R3 and R4 may, when taken together, form a 5- or 6- membered ring of non-metallic atoms].

Description

SPECIFICATION Method for forming cyan dye image FIELD OF THE INVENTION The present invention relates to a method for forming a cyan dye image, and particularly, to a method for forming a cyan dye image by color development of a color photographic light-sensitive material in the presence of a new 2,5-diacylaminophenol cyan coupler. More particularly, the invention relates to a method for forming a cyan dye image in the presence of a new cyan coupler that has high solubility, stability in a dispersion, and good spectal absorption characteristics, which has high dye forming speeds in a color developing solution containing no benzyl alcohol, and which has high color density and long image keeping quality.
BACKGROUND OF THE INVENTION As is well known, according to the subtractive color process, an aromatic primary amine color developing agent reduces exposed silver halide grains, and the resulting oxidized product of the color developing agent is oxidatively coupled in a silver halide emulsion with couplers forming yellow, cyan and magenta dyes. The yellow coupler for forming a yellow dye is generally made of a compound having an open-chain active methylene group; the megenta coupler for forming a magenta dye is generally made of one of pyrazolone, pyrazolinobenzimidazole and indazolone compounds; and the cyan coupler for forming a cyan dye is generally made of a compound having a phenolic or naphtholic hydroxyl group.
Each coupler is added in the silver halide emulsion after it is dissolved in a substantially waterinsoluble high-boiling organic solvent optionally in the presence of an auxiliary solvent, or after it is dissolved in an aqueous alkaline solution. The first method is called the oil droplet dispersion method and the second method is called the alkali dispersion method. The first method is generally said to be better than the second one with respect to light fastness, heat resistance, moisture resistance, graininess or granularity and color sharpness.
Each coupler must meet several basic requirements: first, it must form the desired dye; second, it must have great solubility in the high-boiling organic solvent or alkali; third, it must have good dispersibility and stability in the silver halide photographic emulsion; fourth, the resulting dye must have resistance to light, heat and moisture; fifth, the coupler must have good spectral absorption characteristics, high transparency and high color density; and sixth, the resulting image must be sharp.
The need for improved dye keeping quality such as heat resistance, moisture resistance and light fastness is particularly great for the cyan coupler.
One of the problems the photographic industry has encountered is how to eliminate benzyl alcohol from the color developing solution to prevent pollution. But the fact is a color developing solution free from benzyl alcohol impairs the color developing properties, i.e. the dye forming rate and maximum color density, of the coupler in the silver halide emulsion. This defect is particularly serious with cyan couplers. Hence, there is a great need for a cyan coupler whose color developing properties do not depend on benzyl alcohol, and various studies have been made to develop the desired cyan coupler that also has improved image keeping quality. But as far as the present inventors know, none of the conventional cyan couplers satisfy all of the required properties.
U.S. Patent No. 2,801,171 describes a cyan coupler made of 6- [ a-2,4-di-tert- amylphenoxy)butaneamido ] 2,4-dichlorn-3-methylphenol. This coupler has good light fastness, but as will be apparent from the Examples that are given hereinafter, it has little heat resistance, and in addition, its color developing properties depend on benzyl alcohol so greatly that it is not capable of achieving the desired maximum color density in a benzyl alcohol free color developing solution.
Japanese Patent Application (OPI) No. 109630/78 (the symbol OPI as used herein means an unexamined published Japanese patent appiication) described a coupler wherein a dicarbonyl-amino group is introduced at 2,5-position of phenol and a p-alkylsulfonylphenoxy group or palkylaminosulfonylphenoxy group is introduced at the terminal of the substituent on 5-position.
According to this prior art reference, the coupler has improved dispersion stability during or after application of the emulsion, but as will be apparent from the Examples that are given hereinafter, the color developing properties of the coupler still have great dependence on benzyl alcohol.
German Patent Application (OLS) No. 3,01 7,500 describes a cyan coupler which is an improvement over the coupler of Japanese Patent Application (OPI) No. 109630/78 in that is depends less on benzyl alcohol for its color developing properties. But even this coupler is not capable of meeting all the requirements for the desired cyan coupler.
SUMMARY OF THE INVENTION Therefore, one object of the present invention is to provide a cyan coupler having the desired properties described above.
Another object of the present invention is to provide a cyan coupler that has high solubility in alkali or high-boiling organic solvent and which has good dispersibility and stability in a silver halide color photographic emulsion.
A further object of the present invention is to provide a method of forming a cyan dye image that has good image keeping qualities (i.e. great resistance to heat, light and moisture), and which has high dye forming rate in a benzyl alcohol free color developing solution and which provides a cyan dye image having high color density.
These and other objects of the present invention can be achieved by a method for forming a cyan dye image by exposing and developing of a silver halide color photographic light-sensitive material in the presence of a 2,5-diacylaminophenol cyan coupler, wherein the acylamino group at 2- or 5-position of a phenolic nucleu of said cyan coupler has a substituent represented by the formula (I):
[wherein R1 is
R2 is an alkylene group; R3 is an alkyl group; R4 is a hydrogen atom, an alkyl group or an acyl group; X is c group that can be introduced in the benzene ring as a substituent; n is an integer of 1 to 3;R3 and R4 may, when taken together, form a 5- or 6-membered ring of nonmetallic atoms.] DETAILED DESCRIPTION OF THE INVENTION The alkylene group represented by R2 is preferably a substituted or unsubstituted straight or branched alkylene group having 1 to 20 carbon atoms; the alkyl group represented by R3 is preferably a substituted or unsubstituted straight or branched alkyl group having 1 to 20 carbon atoms; the alkyl group or acyl group represented by R4 is preferably a substituted or unsubstituted straight or branched alkyl or acyl group having 1 to 8 carbon atoms; the group that can be introduced in the benzene ring as a substituent and which is represented by X is illustrated by a substituted or unsubstituted straight or branched alkyl group having 1 to 8 carbon atoms, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, an alkylsulfonamide group, an arylsulfonamide, an acylamino group or a halogen atom such as chlorine or bromine; and n is preferably 1 or 2.
The 2,5-diacylaminophenol cyan coupler according to the present invention is preferably represented by the following formula (II) or (III):
[ wherein R'1, R'2,X' and n are respectively the same as Ra, R2,X and n that are defined in the formula (I); Rs and R's are each a substituted or unsubstituted straight or branched alkyl group {preferably, a fluorine-substituted alkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted branched alkyl group having 4 to 20 carbon atoms (particularly preferably a tert-butyl group)}, an aryl group (preferably a phenyl group or a substituted phenyl group) or a heterocyclic group (preferably, a pyridyl group); Z and Z' are each a hydrogen atom or a group that is capable of eliminating upon coupling reaction with the oxidized product of the color developing agent (preferably, a halogen atom such as chlorine, bromine or fluorine, -OR', -OCOR', -0CONHR', -OSO2NHR', -SR', -N=NR, or a heterocyclic group that has a N atom and which is bonded to the coupling position of the 2,5 diacylaminophenol cyan coupler through the N atom;R' is a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group or a heterocyclic group).] The compound of the formula (I) (hereinunder referred to as the compound of the present invention) is characterized by having an acylamino group both at 2- and 5-position of a phenolic nucleu and is further characterized in that said acylamino group is bonded to the p-alkylsulfonamidophenoxy or p-alkylaminosulfonylphenoxy group (defined in the formula (I)) at phenoxy position. It is believed that the introduction of said group contributes to the various advantageous characteristics of the cyan coupler used in the present invention.
To state more specifically, the coupler of the present invention has high solubility in alkali or highboiling organic solvent, has good dispersion stability in a photographic emulsion, and also has good spectral absorption characteristics as well as high transparency. The color emulsion containing the coupler of the present invention has good image keeping quality (i.e. has high resistance to heat, moisture and light), and it is a pollution-free emulsion whose color developing properties depend little on benzyl alcohol; in other words, it achieves high dye forming rate and color density in a benzyl alcoholfree color developing solution.
As already mentioned, U.S. Patent No. 2,801,1 71, German Patent Application (OLS) No.
3,017,500 and Japanese Patent Application (OPI) No. 109630/78 disclose technical information on cyan couplers, but none of them teaches the coupler of the present invention, and as will be apparent from the Examples that are given hereinafter, the coupler of the present invention exhibits surprising advantages. The coupler of the present invention is particularly characterized by reduced dependency of its color developing properties on benzyl alcohol in a color developing solution, as well as by improved image keeping quality, especially great heat resistance of image.
Typical examples of the cyan coupler according to the present invention are listed below, and it is to be understood that the coupler of the present invention is by no means limited to these examples.
Coupler R1 # R2 R1 Z No. 1 CH3SO2NH- # -CH- # H C18H37 2 # # -CH- # -Cl C12H25 3 # # -CH- # # C10H21 4 n-C4H9SO2NH- # -CH- # -Cl C12H25 5 n-C16H33SO2NH- # -(CH2)3- # -OCH2COOCH3
Coupler R1 # R2 R1 Z No. 6 n-C12H25SO2NH- # -CH- # H C2H5 7 # # -CH- # -Br C12H25 CH3 8 CHSO2NH- # -CH- # H CH3 C15H37 CH3 9 n-C12H25SO2NH- # -C- # -Cl CH3 10 n-C4H9SO2NH- # -C- # H C12H25 11 n-C8H17SO2NH- # -CH- # -Cl C2H5
Coupler R1 # R2 R3 Z No. 12 n-C4H9SO2N- # -CH- # # # C2H5 C10H21 13 n-C16H33SO2N- # -CH- # -OCH2CH2SO2CH3 # CH3CO C2H5 14 n-C16H33SO2NH- # -CH- # # CH3 CH3 15 # # -CH- -C-CH3 # C4H9 C12H25 CH3 16 NSO2- # -CH- -(CF2CH2)-2H -OCH2CONHC3H7(iso) C4H9 C8H17 17 C16H35NHSO2- # -CH- -(CF2CF2)-2H -Cl C2H5
Coupler R1 # R2 R3 Z No. CH3 18 C16H33NHSO2- # -(CH2)2- -C-CH3 # CH3 19 # # -CH- # -Cl C12H25 20 C4H9NHSO2 # -CH- # -OCH2COOC2H5 C12H25
Coupler R1' # R2' R3' Z' No. CH3 21 -NHSO2CH3 # -CH- CH2-C- H C16H37 CH3 22 -NHSO2C4H9(n) # -CH- # Cl C12H25 23 -NHSO2C16H33(n) # -(CH2)3 # # CH3 24 -NSO2C16H33(n) # -C- # # C2H5 CH3 25 -NSO2C4H9(n) # -CH- # # C4H9 C10H21 C4H9 26 -SO2N # -CH- # -Cl C4H9 C4H9
Coupler R' # R2' R3' Z No. CH3 27 -SO2N # -CH2- # # CH3 28 -SO2NHC4H9 # -(CH2)3- # # 29 -SO2NHC1635 # -CH- # -OCH2CH2SO2CH3 C2H5
Three typical examples of the method of producing the cyan coupler of the present invention are given below.
SYNTHESIS EXAMPLE 1 (cyan coupler 2 of the present invention) Synthesis of 2-(4-ch loro)benzoylamido-4-ch lorn-5-ja-(4-trimethylenesulfonamido-3- methyl)phenoxy}tetradecaneamidophenol 2-(4-Chloro)benzoylamido-4-chloro-5-aminophenol (30 g) was added to a mixture of 300 ml of ethyl acetate and 9.6 cc of pyridine under stirring to form a uniform solution. Under continued stirring at room temperature, a solution of 56 g of (a-(4-trimethylenesulfonamido-3- methyl)phenoxyjtetradecanoic acid chloride in 100 ml of ethyl acetate was added dropwise to the previously prepared solution over a period of 30 minutes. The mixture was left to stand at room temperature for 30 minutes, and the completion of the reaction was confirmed by thin-layer chromatography.The reaction liquor was mixed with water, extracted with ethyl acetate, and washed with water to separate the oil layer, which was dried with anhydrous sodium sulfate. After distilling the solvent off under vacuum, the residue was purified by column chromatography and crystallized with ethyl acetate/n-hexane. A white solid (34 g) having a m.p. of 113-117 C was obtained.
Elemental analysis 0% H% N% S% 01% Calculated: 60.65 6.47 5.73 4.38 9.68 Found: 59.96 6.31 5.82 4.43 9.59 SYNTHESIS EXAMPLE 2 (cyan coupler 4 of the present invention) Synthesis of 2-benzoylamido-4-chloro-5-{-(2-ch loro-4 butylsulfonamido)phenoxyjtetradecanamidophenol 2-Benzoylamido-4-chloro-5-aminophenol (26 g) was added to a mixture of 250 ml of ethyl acetate and 9.6 cc of pyridine under stirring to form a uniform solution. Under continued stirring at room temperature, a solution of 56 g of -(2-chlorn-4-butylsulfonamido)phenoxytetradecanoic acid chloride in 100 ml of ethyl acetate was added dropwise to the previously prepared solution over a period of 30 minutes.The mixture was left to stand at room temperature for 30 minutes, and completion of the reaction was conformed by thin-layer chromatography. The reaction liquor was mixed with water, extracted with ethyl acetate, and washed with water to separate the oil layer, which was dried with anhydrous sodium sulfate. After distilling the solvent off under vacuum, the residue was purified by column chromatography and crystallized with ethyl acetate/n-hexane. A white solid (24 g) having a m.p. of 108111 C was obtained.
Elemental analysis C% H% N% S% 01% Calculated: 63.54 7.06 6.01 4.58 5.07 Found: 63.61 6.93 6.21 4.49 5.13 SYNTHESIS EXAMPLE 3 (cyan coupler 7 of the present invention) Synthesis of 2-(3-phenoxywarbonyl)benzoylamido-4-bromo-5-{(2-chloro-4- tetramethylenesulfonamido)phenoxy}tetradecaneamide 2-(3-Phenoxycarbonyl)benzoylamido-4-bromo-5-aminophenol (43 g) was added to a mixture of 400 ml of ethyl acetate and 9.6 cc of pyridine under stirring to form a uniform solution. Under continued stirring at room temperature, a solution of 56.5 g of a-(2-chloro-4-tetramethylenesulfonamido)- phenoxytetradecanoic acid chloride in 100 ml of ethyl acetate was added dropwise to the previously prepared solution over a period of 30 minutes. The mixture was left to stand at room temperature for another 30 minutes, and the completion of the reaction was confirmed by thin-layer chromatography.
The reaction liquor was mixed with water, extracted with ethyl acetate, and washed with water to separate the oil layer, which was dried with anhydrous sodium sulfate. After distilling the solvent off under vacuum, the residue was purified by column chromatography and crystallized with ethyl acetate/n-hexane. A white solid (37 g) having a m.p. of 98--1030C was obtained.
Elemental analysis C% H% N% S% Br% Calculated: 61.32 5.97 4.88 3.72 9.27 Found: 60.95 6.02 5.01 3.63 9.09 The cyan coupler of the present invention may be incorporated in a color emulsion and used as an oil-protected coupler. Such coupler can be prepared by a known method: for example, one or more of the couplers according to the present invention are dissolved in a high-boiling organic solvent having a -boiling point of 1 7500 or more such as tricresyl phosphate or dibutyl phthalate and/or a low-boiling solvent such as butyl acetate or butyl propionate, and then, the solution is mixed with an aqueous gelatin solution containing a surfactant, and the mixture is emulsified by a high-speed mixer or colloid mill, and silver halide grains are put into the resulting emulsion to thereby produce a silver halide emulsion suitable for use in the present invention.
The coupler of the present invention may be used as a coupler-in-developer type. But a better result is obtained with a coupler-in-emulsion type photographic photosensitive material because the thickness of the photosensitive layer in which the coupler is incorporated can be reduced, a sharper color image is obtained, and the coupler has no adverse effect on color development and prevents color stain because of its high reactivity with the color developer. As mentioned before, the dye produced by using the coupler of the present invention has good spectral absorption characteristics.
If the coupler of the present invention is a nondiffusion coupler wherein the cyan coupler residue is nondiffusible and the split-off group is diffusible, it is suitable for use in the diffusion transfer process.
Each group in the coupler can be provided with diffusibility by selecting a low-molecular group and/or introducing a water-soluble group such as sulfonate group. Nondiffusibility can be given to each group by introducing a long-chain aliphatic hydrocarbon residue and/or selecting a relatively high-molecular group.
The silver halide emulsion containing the coupler of the present invention is red-sensitive, and a red-sensitive emulsion layer can be formed on a photographic base by applying such emulsion onto the base and drying the web.
The silver halide emulsion according to the present invention may contain any of the silver halides that are employed in the conventional silver halide emulsion, such as silver bromide, silver chloride, silver iodobromide, silver chlorobromide and silver chloroiodobromide.
The silver halide emulsion suitable for the present invention can be prepared by any conventional method or any of the methods described in prior art references such as Japanese Patent Publication No.
7772/71 and U.S. Patent No.2,592,250. The method described in Japanese Patent Publication No.
7772/71 is conventionally used to prepare a "conversion emulsion", and in this method, an emulsion of silver salt grains at least part of which silver salt has greater solubility than silver bromide, and at least part of said grains are then converted to silver bromide or silver iodobromide grains. The method described in U.S. Patent No. 2,592,250 is conventionally used to prepare a "Lippmann emulsion" comprising fine silver halide grains having an average size of 0.1 y or less.
The silver halide emulsion of the present invention can be chemically sensitized with various sensitizers such as sulfur sensitizer, e.g. allyl thiocarbamide, thiourea or cystine; selenium sensitizer, e.g.
activated or inert selenium sensitizer; reduction sensitizer, e.g. stannous salt, or polyamin; noble metal sensitizer, e.g. gold sensitizer (more specifically, potassium aurithiocyanate, potassium chloroaurate or 2-aurosulfobenzthiazole methyl chloride; and water-soluble salts of ruthenium, rhodium and irridium, e.g. ammonium palladate, potassium chloroplatinate and sodium chloropalladide. These sensitizers may be used alone or in combination.
The silver halide emulsion of the present invention may contain various known photographic additives.
To provide sensitivity to the sensitive wavelength region necessary for a red-sensitive emulsion, the silver halide used in the present invention can be subjected to spectral sensitization by a suitable sensitizing dye. Various spectral sensitizing dyes can be used either alone or in combination. Typical spectral sensitizing dyes that can be used in the present invention with advantage include cyanine dyes, merocyanine dyes and complex cyanine dyes of the type described in U.S. Patents Nos. 2,269,234, 2,270,378,2,442,710, 2,454,629 and 2,776,280.
The color developing solution that can be used in the present invention contains an aromatic primary amine color developing agent which is typified by p-phenylenediamine compounds, such as diethyl-p-phenylenedia mi ne hydrochloride, monomethyl-p-phenylenediamine hydrochloride, di methylp-phenylenediamine hydrochloride, 2-amino-5-diethylaminotoluene hydrochloride, 2-amino-5-(N-ethyl N-dodecylamino)-toluene, 2-amino-5-(N-ethyl-N--methanesulfonamidoethyl)-aminotoluene sulfonate, 4-(N-ethyl-N-P-methanesulfonamidoethylam 4-(N-ethyl-N-P-hydroxyethylamino)aniline and 2-a mino-5-(N-ethyi-N-p-methoxyethyl) ami notoluene.
These color developing agents are used alone or in combination with themselves or, if necessary, with a black-and-white developing agent such as hydroquinone. The color developing solution generally contains an alkali agent such as sodium hydroxide, ammonium hydroxide, sodium carbonate, sodium sulfate or sodium sulfite, and it may further contain various additives such as alkaki metal halide, e.g.
potassium bromide, and a development control agent, e.g. citrazinic acid.
The color photographic photosensitive material of the present invention is first exposed to light and color-developed by a conventional coupler-in-emulsion type color developing process, but in an exceptional case, such as certain type of the diffusion transfer process, the color developing solution may be incorporated in the image-receiving material. In this exceptional case, either alkali agent or color developing agent is incorporated in the image-receiving material, and the material is developed with a solution containing the other agent, i.e. color developing agent or alkali agent.
A typical color developer for the coupler in emulsion type has the following formulation.
(Formulation of color developer) 4-Amino-3-methyl-N-ethyl-N-(j-methanesulfon- 5.0 g amidoethyl)-aniline sulfate Anhydrous sodium sulfite 2.0 g Sodium carbonate monohydrate 50 g Potassium bromide 1.0 g Potassium hydroxide 0.55 g Water to make one liter When a silver halide is developed with such color developer, the oxidation product of the color developing agent is produced, and the coupler of the present invention that is contained in the color emulsion used in the present invention reacts with said oxidation product to form a cyan dye.
After the color development, the silver halide color photographic photosensitive material of the present invention is subjected to a conventional photographic processing using any of the following processing solutions, such as a stop solution containing an organic acid, a stop fixer containing an organic acid and a fixing component such as sodium thiosulfate or ammonium thiosulfate, a fixing solution containing a fixing component such as sodium thiosulfate or ammonium thiosulfate, a bleaching solution mainly consisting of a ferric salt of aminopolycarboxylic acid and alkali halide, a bleach-fix bath containing a ferric salt of aminopolycarboxylic acid and a fixing component such as sodium thiosulfate or ammonium thiosulfate, and a stabilizing solution, as well as subsequentwashing and drying.
A typical example of the photographic processing that can be applied to a coupler-in-emulsion type color negative photosensitive material according to the present invention is shown below.
(Processing scheme) Processing steps (3300) time color development 3 min 1 5 sec bleaching 6 min 30 sec washing 3 min 15 sec fixing 6 min 30 sec washing 3 min 1 5 sec stabilizing 1 min 30 sec The following processing solutions can be used in the respective steps.
(Formulation of the color developer) 4-Ami no-3-methyl-N-ethyl-N-(P-hydroxyethyl)- 4.8 g aniline sulfate Anhydrous sodium sulfite 0.149 Hydroxyamine.1/3 sulfate 1.98g Sulfuric acid 0.74 mg Anhydrous potassium carbonate 28.85 g Anhydrous potassium hydrogencarbonate 3.46 g Anhydrous potassium sulfite 5.10g Potassium bromide 1.169 Sodium chloride 0.14 9 Nitriloacetic acid trisodium salt monohydrate 1.20 g Potassium hydroxide 1.48 g Water to make one liter (Formulation of the bleaching solution) Ethylenediaminetetraacetic acid iron 100 g ammonium salt Ethylenediaminetetraacetic acid lOg diammonium salt Ammonium bromide 150 g Glacial acetic acid 10 ml Water to make one liter, and ammonia water to adjust the pH to 6.0 (Formulation of fixer) Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.6 g Sodium metasulfite 2.3 g Water to make one liter, and acetic acid to adjust the pH to 6.0 (Formulation of stabilizing solution) Formalin (as 30% aqueous solution) 1.5 ml Konidaks (product of Konishiroku Photo 7.5 ml Industry Co., Ltd.) Water to make one liter A typical example of the photographic processing that can be applied to a coupler-in-emulsior type color reversal photosensitive material according to the present invention is shown below.
(Processing scheme) Processing steps (240C) time First development 5 min washing 4 min exposure color development 3 min washing 4 min bleaching 4 min fixing 4 min washing 10 min The first developer, color developer, bleaching solution and fixing solution had the following respective formulations.
(Formulation of the first developer) Anhydrous sodium sulfite 8.0 g P henidone 0.35 g Anhydrous sodium sulfite 37.0 g Hydroquinone 5.5 9 Anhydrous sodium carbonate 28.2g Sodium thiocyanate 1.38g Anhydrous sodium bromide 1.30 g Potassium iodine (as 0.1% aqueous solution) 13.0 ml Water to make one liter (pH: 8.9) (Formulation of the color developer) Benzyl alcohol 5.0 ml Sodium hexametaphosphate 2.5 g Anhydrous sodium sulfite 1.9 9 Sodium bromide 1.4 9 Potassium bromide 0.5 g Borax (Na2B4O7.1 OH2o) 39.1 g N-ethyl-N-p-methanesulfonamidoethyl-4- 5.0 g amino-3-methylaniline sulfonate Water to make one liter, and sodium hydroxide to adjust the pH to 10.80 (.Formulation of the bleaching solution) Anhydrous sodium bromide 43.0 g Red prussiate 165.or Borax (Na2B4O7.1 0H20) 1.2 g Water to make one liter (Formulation of the fixing solution) Sodium thiosulfate pentahydrate 200.0 g Anhydrous sodium sulfate 100.or Anhydrous disodium phosphate 15.0g Water to make one liter A typical example of the photographic processing that can be applied to a coupler-in-emulsion type color positive photosensitive material according to the present invention is shown below.
(Processing scheme) Processing steps (30 C) time color development 3 min 30 sec Bleach-fixing 1 min 30 sec washing 2 min stabilizing 1 min The following processing solutions can be used in the respective steps.
(Formulation of color developer (1)) 4-Amino-3-methyl-N-ethyl-N-(p-methane- 5.0 g sulfonamidoethyl)-aniline sulfate Sodium hexametaphosphate 2.5 g Anhydrous sodium sulfite 1.85 g Sodium bromide 1.4 g Potassium bromide 0.5g Borax 39.1 g Water to make one liter, and sodium hydroxide to adjust the pH to 10.30 (Formulation of color developer (2)) 4-Amino-3-methyl-N-ethyl-N-(j5-methane- 5.0 g sulfonamidoethyl)-aniline sulfate Benzyl alcohol 15.0 ml Sodium hexametaphosphate 2.5 g Anhydrous sodium sulfite 1.85 g Sodium bromide 1.4 g Potassium bromide 0.5 9 Borax 39.19 Water to make one liter, and sodium hydroxide to adjust the pH to 10.30 The color developer (1) is free of benzyl alcohol, and the color developer (2) has a conventional formulation containing benzyl alcohol. When the process of the present invention is used to process a coupler-in-emulsion type color positive photo-sensitive material either color developer can be used, but to prevent pollution, use of the color developer (1) is preferred, and according to the process of the present invention, good photographic characteristics can be achieved by using this preferred color developer (1).
(Formulation of bleach-fix bath) Ethylenediaminetetraacetic acid iron 61.0 g ammonium salt Ethylenediaminetetraacetic acid 5.0g diammonium salt Ammonium thiosulfate 124.5 g Sodium metabisulfite 13.3 g Anhydrous sodium sulfite 2.7 g Water to make one liter (Formulation of stabilizer) Glacial acetic acid 20 ml Water to make one liter, and sodium acetate to adjust the pH to 3.5 4.0 The image forming method of the present invention can also be applied with advantage to the photosensitive materials that are used in the "image amplification" which are described in Japanese Patent Publication 46419/74, Japanese Patent Applications (OPI) Nos. 7929/76,16023/76 and 36136/76.
The present invention is now described in greater detail by reference to the following examples which are given here for illustrative purposes only and are by no means construed as limiting the scope of the present invention.
EXAMPLE 1 The cyan couplers identified in Table 1 below by the number used in the foregoing list of specific examples of the cyan couplers of the present invention and the comparative couplers (A), (B) and (C) identified below were used. Each coupler (109) was added to a mixture of 2.5 ml of dibutyl phthalate and 20 ml of ethyl acetate, and the mixture was heated at 600C until a uniform solution was obtained.Each of the solutions was mixed with 5 ml of a 10 g aqueous solution of Alkanol B (alkylnaphthalenesulfonate produced by Du Pont) and 200 ml of a 5% aqueous gelatin solution, and the mixture was emulsified by a colloid mill to prepare a dispersion of each coupler.The coupler dispersion was mixed with 500 ml of a gelatin-silver chlorobromide (containing 20 mol% silver bromide) emulsion, and the mixture was spread on a polyethylene-coated paper base and dried. In this manner, seven silver halide color photographic photosensitive materials each having a stable emulsion coating were prepared. The respective materials were identified as Samples Nos. 1 to 7. The seven samples were exposed through an optical wedge by a conventional method, and subsequently subjected to a color development to form a cyan color developed image according to the stated processing scheme for coupler-in-emulsion type color positive photosensitive material. In the processing, two color developers were used: one of them contained benzyl alcohol and was the same as the color developer (2), and the other contained no benzyl alcohol and was the same as the color developer (1). The images were checked for their resistance to light, heat and moisture. The results are shown in Table 1.
TABLE 1
Color developer (2) Color developer (1) Sample Specific max.density Specific max.density No. Cyan coupler sensitivity Fog (Dm) sensitivity Fog (Dm) # max.
1 Cyan coupler of the 95 0.02 2.15 80 0.02 2.00 657 present invention (2) 2 Cyan coupler (4) 100 0.02 2.20 85 0.02 2.05 666 3 Cyan coupler (16) 100 0.02 2.20 90 0.04 2.10 683 4 Cyan coupler (22) 95 0.02 2.15 80 0.02 2.00 664 5 Comparative cyan 100 0.03 2.20 55 0.03 1.52 660 coupler [A] 6 Comparative cyan 90 0.02 2.10 70 0.02 1.90 655 coupler [B] 7 Comparative cyan 95 0.02 2.15 75 0.02 1.95 655 coupler [C] In Table 1, the figures in the column of "specific sensitivity" are the values relative to the sinsitivity (100) of the sample No. 5 that contained the comparative coupler (A) and which was processed with the color developer (2). The structures of the comparative couplers (A), (B) and (C) are shown below.
Comparative coupler (A): 6- [ a-(2,4-Di-tert-amylphenoxy)butaneamido ] 2,4-di-chloro-3-methylphenol (described in U.S.
Patent No.2,801,171) Comparative coupler (B): 2-Benzoyiamido-4-chloro-5- [ a-(4-butylsu Ifonamidophenoxy)tetradeca nea mido ] phenol (described in Japanese Patent Application (OPI) No. 1 09630/78) Comparative coupler (C): 2-Benzoylamido-4-chloro-5- [ a-(4-(p-toluenesulfonamido)phenoxy)-tetradecaneamido ] phenol (described in Germany Patent Application (OLS) No. 3,017,500) As is clear from Table 1, the samples processed by the image forming method of the present invention had more satisfactory spectral absorption characteristics, and the color images formed by processing in the benzyl alcohol free color developer system had a greater maximum density than those obtained by using the comparative couplers (A), (B) and (C).
EXAMPLE 2 Seven cyan colored image forming photosensitive materials (Samples Nos. 8 to 14) were prepared as in Example 1. The images formed on the respective samples were checked for their resistance to light, heat and moisture. The results are shown in Table 2 below.
TABLE 2
TABLE 2 Color developer (2) Color developer (1) Light Moisture Heat Light Moisture Heat Sample fastness resistance resistance fastness resistance resistance No. Coupler (7th day) (14th day) (14th day) (7th day) (14th day) (14th day) (%) (%) (%) (%) (%) (%) 8 Cyan coupler of the 83 100 98 88 100 98 present invention (2) 9 Cyan coupler (4) 90 100 98 90 100 98 10 Cyan coupler (7) 85 100 98 85 100 98 11 Cyan coupler (22) 90 100 98 89 100 98 12 Comparative cyan 90 75 65 91 72 64 coupler [A] 13 Comparative cyan 72 100 98 71 100 98 coupler [B] 14 Comparative cyan 80 100 98 81 100 98 coupler [C] In Table 2, the figures in the column of "light fastness" indicate the residual density of each image that was exposed to a xenon lamp in a fade-0-meter for 200 hours, and the respective values are relative to the density (100) before the exposure. The figures in the column of "moisture resistance" indicate the residual density of each image that was left at 500C and r.h. 80% for 2 weeks, and the respective values are relative to the density (100) before the test. The figures in the column of "heat resistance" indicate the residual density of each image that was left at 770C for 2 weeks, and the respective values are relative to the density (100) before the test.
As is clear from Table 2, the comparative coupler (A) exhibited high resistance to light but its resistance to heat was not great. The comparative couplers (B) and (C) were more heat-resistant than the comparative coupler (A), but the images they formed by development in a benzyl alcohol-free developing solution were not satisfactorily lightfast.
On the other hand, the cyan couplers 2, 4, 7 and 22 of the present invention were as heat resistant as the comparative couplers (B) and (C), and proved more lightfast.
EXAMPLE 3 The cyan coupler 5 of the present invention (10 g) was added to a mixture of 25 ml of dibutyl phthalate and 20 ml of ethyl acetate, and the resulting mixture was heated at 6000 to form a complete solution. The solution was mixed with 5 ml of a 10% aqueous solution of Alkanol B and 200 ml of 5% aqueous gelation, and the mixture was emulsified by a colloid mill to prepare a cyan coupler dispersion.
The dispersion was added to 500 g of a high-sensitivity negative silver iodobromide (containing 6.0 mol% of silver iodide), and the emulsion was spread on a cellulose acetate film base and dried to prepare a silver halide photographic photosensitive material having a stable silver halide emulsion coating. The material was identified as Sample No.15. Sample No. 1 6 was prepared in the same manner except that the cyan coupler 5 was replaced by the comparative coupler (A). Both samples were exposed as in Example 1 and subjected to color development by the stated processing scheme for the coupler-in-emulsion type color negative photographic material. The cyan colored imaged produced were checked for their photographic characteristics. The results are shown in Table 3.
TABLE 3 relative Sample No. cyan coupler sensitibity max. density max 15 cyan coupler 5 140 2.50 655 16 comparative coupler (A) 57 1.51 660 As is clear from Table 3, the sample using the cyan coupler of the present invention had a greater maximum density, and it produced a more transparent cyan negative image.
EXAMPLE 4 Six samples of gelatin dispersion having the below indicated formulation were prepared using the cyan couplers 1 , 2, 4, 6 and 9 of the present invention and the comparative coupler (D) (identified below), respectively.
Coupler 4.0 g 2,4-Di-tert-amylphenol 1.33 g Ethyl acetate 12g Gelatin (29.1 ml of 1.25% gelatin) 3.64g Sodium triisopropylnaphthalene-1 -sulfonate 4 ml Water 9 ml Each dispersion was shaped into noodles, washed, fused again, and checked for the presence of a coupler crystal under a microscope (125 x). The dispersion was immersed in a water bath (40 C) for 8 hours and examined for the presence of coupler crystal under a microscope (125 x). All dispersions were rated for the coupler crystal stability before and after the immersion in the water bath. The results are shown in Table 4 below. The rating scheme was as follows: (S) ... satisfactory, (U) ... unsatisfactory and (0) . . questionable.The rating (S) was given when the dispersion contained little or no crystal before the immersion and if there was no change in the crystallinity after the immersion. The rating (U) was given when the dispertion was found to contain a considerably number of crystals. The rating (Q) was given when the number of crystals was in between.
Comparative coupler (D): 2-Benzoylamido-4-chlorn-5- [ ar-(3-methyl-4-(-p-toluenesulfonyl) ethylsulfonamideiphenoxy ] tetradecaneamidophenol TABLE 4 Crystallinity before immersion in after immersion Cyan coupler water bath cyan coupler 1 (S) (S) 2 (S) (S) 4 (S) (S) 6 (s) (S) 9 (S) (S) comparative coupler (D) (S) (Q) As is clear from Table 4, the comparative coupler (D) had a tendency to crystallize upon immersion in the water bath. But the cyan couplers of the present invention had little or no tendency to crystallise when dispersed in the same gelatin emulsion.

Claims (12)

CLAIMS:
1. A method of forming a cyan dye image which comprises developing an exposed silver halide color photographic light-sensitive material in the presence of a 2,5-diacylaminophenol cyan coupler, wherein the acylamino group at 2- or 5-position of the phenolic nucleus of said cyan coupler has a substituent represented by the formula (I):
wherein R is a
R2 is an alkylene group; R2 is an alkyl group; R4 is a hydrogen atom, an alkyl group or an acyl group; or R2 and R4 together form a 5- or 6-membered ring of non-metallic atoms with the atom(s) to which they are attached; X is a substituent; n is an integer of 1 to 3.
2. A method according to claim 1, wherein the cyan coupler is represented by the following general formula (II) or (III):
wherein R',, R'2, X' and n are as defined under R1, R2,X and n, respectively, in claim 1; Rs and R'5 are each independently substituted or unsubstituted straight or branched alkyl group, and aryl group or a heterocyclic group; Z and Z' are each independently a hydrogen atom or a group that is capable of splitting off upon coupling with an oxidized product of the color developing agent.
3. A method according to claim 1 or 2 wherein Z and Z' are each independently a hydrogen atom, a halogen atom, -OR', -OCOR', -OCONHR', -OSO2NHR', -SR', -N=NR', or a heterocyclic group.
4. A method according to any one of claims 1 to 3 wherein X or X' is an alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, an alkylsulfonamido group, an arylsulfonamido, an acylamino group or a halogen atom.
5. A method according to claim 1 wherein the said cyan coupler is one specifically identified herein.
6. A method according to any one of the preceding claims wherein the said cyan coupler is present in a silver halide emulsion of the silver halide material.
7. A method according to claim 1 substantially as described in any one of Examples 1 to 4.
8. A cyan dye image whenever formed by a method as claimed in any one of the preceding claims.
9. A silver halide color photographic light-sensitive material comprising a 2,5-diacylaminophenol cyan coupler as defined in claim 1.
10 A light sensitive material according to claim 9 wherein the 2,5-diacylaminophenol cyan coupler is one as defined in any one of claims 3 to 5.
11. A silver halide color photographic light-sensitive material according to claim 9 substantially as hereinbefore described.
12. A 2,5-dicylaminophenol cyan coupler, the acylamino group at the 2- or 5-position of the phenolic nucleus having a substituent represented by the formula:
wherein Ra, R2, X and n are as defined in claim 1.
GB8207292A 1981-03-23 1982-03-12 Sulphonamido-containing 2,5- diacylaminophenol cyan couplers for cyan dye imaging Withdrawn GB2098600A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4500635A (en) * 1983-03-14 1985-02-19 Fuji Photo Film Co., Ltd. Color photographic silver halide light-sensitive material
US4557999A (en) * 1983-02-09 1985-12-10 Fuji Photo Film Co., Ltd. Silver halide color photographic light-sensitive material

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5961835A (en) * 1982-09-30 1984-04-09 Konishiroku Photo Ind Co Ltd Color photographic sensitive silver halide material
JPS59198454A (en) * 1983-04-25 1984-11-10 Konishiroku Photo Ind Co Ltd Method for forming dye image
US4916051A (en) * 1987-04-07 1990-04-10 Konica Corporation Silver halide color photographic light-sensitive material
JPH026272U (en) * 1988-06-24 1990-01-16
US6197490B1 (en) * 1999-12-28 2001-03-06 Eastman Kodak Company Photographic element, compound, and process
US6197491B1 (en) * 1999-12-28 2001-03-06 Eastman Kodak Company Photographic element, compound, and process

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4557999A (en) * 1983-02-09 1985-12-10 Fuji Photo Film Co., Ltd. Silver halide color photographic light-sensitive material
US4500635A (en) * 1983-03-14 1985-02-19 Fuji Photo Film Co., Ltd. Color photographic silver halide light-sensitive material

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