EP0365252A2 - Matériau photographique couleur à l'halogénure d'argent sensible à la lumière pour faire des négatifs couleurs - Google Patents

Matériau photographique couleur à l'halogénure d'argent sensible à la lumière pour faire des négatifs couleurs Download PDF

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Publication number
EP0365252A2
EP0365252A2 EP89310584A EP89310584A EP0365252A2 EP 0365252 A2 EP0365252 A2 EP 0365252A2 EP 89310584 A EP89310584 A EP 89310584A EP 89310584 A EP89310584 A EP 89310584A EP 0365252 A2 EP0365252 A2 EP 0365252A2
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EP
European Patent Office
Prior art keywords
group
silver halide
sensitive
formula
inhibit
Prior art date
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EP89310584A
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German (de)
English (en)
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EP0365252A3 (en
Inventor
Yukio Ohya
Yoshiro Ito
Syoji Matsuzaka
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Konica Minolta Inc
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Konica Minolta Inc
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Publication of EP0365252A2 publication Critical patent/EP0365252A2/fr
Publication of EP0365252A3 publication Critical patent/EP0365252A3/en
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/32—Colour coupling substances
    • G03C7/3225—Combination of couplers of different kinds, e.g. yellow and magenta couplers in a same layer or in different layers of the photographic material
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/3003—Materials characterised by the use of combinations of photographic compounds known as such, or by a particular location in the photographic element
    • 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
    • G03C7/3029—Materials characterised by a specific arrangement of layers, e.g. unit layers, or layers having a specific function
    • G03C2007/3034—Unit layer
    • 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
    • G03C7/36—Couplers containing compounds with active methylene groups
    • G03C7/38—Couplers containing compounds with active methylene groups in rings

Definitions

  • the present invention relates to a silver halide color photographic light-sensitive material for making color negatives, and more particularly to improvements in the characteristics comprising the sharpness, processing stability, preservability and formalin resistance of a silver halide color photographic light-sensitive material.
  • a presently commercially available color negative film for camera-exposure use is of a multilayer construction comprising blue, green and red-sensitive emulsion layers, each of which layers is comprised of a plurality of high and low-speed layers, in combination with various additives and auxiliary layers to obtain a wide latitude and excellent graininess and sharpness.
  • a standard light-sensitive material of the ISO speed 100 type leaves no more room for a large improvement in the graininess by reducing the silver halide grain size even if such a multi-layer construction is further tried, and besides, it is very difficult to retain the sharpness and other important photographic characteristics, in the practicable range.
  • pyrazoloazole-type magenta couplers such as pyrazolopyrazole, pyrazolotriazole, etc., are known to be excellent in the formalin resistance, but the fact that they are capble of improving the preservability of a light-sensitive material before being exposed have not yet been known at all.
  • a silver halide color photographic light-sensitive material for making color negatives comprising a support having thereon at least a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, a red-sensitive silver halide emulsion layer, in which the green-sensitive emulsion layer is comprised of a single layer containing a DIR coupler and a magenta coupler represented by the following Formula I: wherein Z represents a group of nonmetallic atoms necessary to form a nitrogen-containing heterocyclic ring, provided that the ring formed by Z may have a substituent; X is a hydrogen atom or a group capable of being split off upon the reaction with the oxidation product of a color developing agent; and R is a hydrogen atom or a substituent.
  • a single layer mentioned above includes also a plurality of emulsion layers provided as serial layers which are equal in the type of the coupler contained therein, the silver halide grain size, the silver halide composition and crystal habit, and the ratio of the coupler to the silver halide.
  • each of the green-sensitive and blue-sensitive silver halide emulsion layers is of a single layer, and more preferably, each of the green-sensitive, blue-sensitive and red-sensitive silver halide emulsion layers is of a single layer.
  • the total dry thickness of the layers is preferably 20 to 3 ⁇ m, and more preferably 15 to 5um.
  • the exposure latitude of the silver halide emulsion layer being a single layer is preferably not less than 3.0.
  • a useful means to widen the latitude to this extent is a method of using mixed silver halide grains different in the sensitivity.
  • the method includes, for example, a method of using mixed silver halide emulsions different in the average grain size, and a method of incorporating a desensitizer into at least a part of silver halide grains.
  • the silver halide emulsions different in the average grain size to be mixed in order to obtain a wide latitude are preferably a combination of a silver halide emulsion having the largest average grain size of 0.2 to 2.Ou. m and a silver halide emulsion having the smallest average grain size of 0.05 to 1 .Ou. m, and further one or more kind of silver halide emulsion having a medium average grain sizemay also be used in combination.
  • the average grain size of the silver halide emulsion having the largest average grain size is preferably 1.5 to 40 times that of the silver halide grains having the smallest average grain size.
  • various agents including antifoggants, stabilizers, desensitizing dyes and the like may be used. Above all, a metallic ion doping method is preferred.
  • the metallic ion to be used in the doping includes metallic ions such as of Cu, Cd, Zn, Pb, Fe, TI, Rh, Bi, Ir, Au, Os, Pd, etc. Preferred among these are Cu, Rh and Os, and the most preferred is Rh. These metallic ions may be used in the form of, e.g., halogeno complex salts, and also in combination of two or more of them. pH of the AgX suspension in doping is preferably not more than 5.
  • the doping amount of these metallic ions depends on the kind of a metallic ion, the silver halide grain size, the doping position of a metallic ion, the objective sensitivity etc., but is preferably 10- 17 to 10- 2 mole per mole of AgX, and particularly 10- 16 to 10- 4 .
  • the silver halide grain may be given any arbitrary sensitivity.
  • the foregoing antifoggant or stabilizer usable as a desensitizer includes azoles such as benzothiazolium salts, indazoles, triazoles, benzotriazoles and benzimidazoles; mercapto-substituted heterocyclic compounds such as mercaptotetrazoles, mercaptothiazoles, mercaptothiadiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles and mercaptopyrimidines; azaindenes such as tetraazaindenes and pentaazaindenes, nucleic acid decomposition products such as adenine and guanine; benzenethiosulfonic acids; and thioketo compounds.
  • azoles such as benzothiazolium salts, indazoles, triazoles, benzotriazoles and benzimidazoles
  • mercapto-substituted heterocyclic compounds such
  • the foregoing desensitizing dye includes cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes.
  • a position where the desensitizing dye is to be present, from the standpoint of the preservability of a light-sensitive material and the retention stability of a coating liquid, is preferably the inside of the silver halide grain, where the desensitizing dye may be contained in to be either uniformly distributed or present locally in the central or intermediate portion of the grain, or may be present so as to be gradually reduced toward outside from the central portion of the grain.
  • magenta coupler represented by the foregoing Formula I is explained:
  • Z is a group of non-metallic atoms necessary to form a nitrogen-containing heterocyclic ring.
  • the ring formed by Z may have a substituent.
  • X is a hydrogen atom or a substituent capable of being split off upon the reaction with the oxidation product of a color developing agent.
  • R is a hydrogen atom or a substituent.
  • the substituent represented by R although not particularly restricted, is typified by an alkyl group, an aryl group, an anilino group, an acylamino group, a sulfonamido group, an alkylthio group, an arylthio group, an alkenyl group and a cycloalkyl group.
  • R is also typified by a halogen atom, a cycloalkenyl group, an alkinyl group, a heterocyclic.
  • a sulfonyl group a sulfinyl group, a phosphonyl group
  • an acyl group a carbamoyl group, a sulfamoyl group, a cyano group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, a siloxy group, an acyloxy group, a carbamoyloxy group, an amino group, an alkylamino group, an imido group, an ureido group, a sulfamoylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic thio group, a spiro compound residue and a bridged hydrocarbon compound residue.
  • the alkyl group represented by R is preferably one having 1 to 32 carbon atoms and may be either straight-chain or branched-chain.
  • the aryl group represented by R is preferably a phenyl group.
  • the acylamino group represented by R includes an alkylcarbonylamino group and an arylcarbonylamino group.
  • the sulfonamido group represented by R includes an alkylsulfonylamino group and an arylsulfonylamino group.
  • the alkyl component and aryl component of the alkylthio group and arylthio group represented by R include the above alkyl and aryl groups represented by R.
  • the alkenyl group represented by R includes one having 2 to 32 carbon atoms, and the cycloalkenyl group is one having 3 to 12 carbon atoms, particularly preferably to 7 carbon atoms.
  • the alkenyl group may be either straight-chain or branched-chain.
  • the cycloalkenyl group represented by R includes one having preferably 3 to 12 carbon atoms, and particularly 5 to 7 carbon atoms.
  • the sulfonyl group represented by R includes an alkylsulfonyl group, an arylsulfonyl group.
  • the sulfinyl group represented by R includes an alkylsulfinyl group, an arylsulfinyl group.
  • the phosphonyl group includes an alkylphosphonyl group, an alkoxyphosphonyl group, an aryloxyphosphonyl group, an arylphosphonyl group.
  • the acyl group includes an alkylcarboinyl group, an arylcarbonyl group.
  • the carbamoyl group includes an alkylcarbamoyl group, an arylcarbamoyl group.
  • the sulfamoyl group includes an alkylsulfamoyl group, an arylsulfamoyl group.
  • the acyloxy group includes an alkylcarbonyloxy group, an arylcarbonyloxy group.
  • the carbamoyloxy group includes an alkylcarbamoyl group, an arylcarbamoyloxy group.
  • the ureido group includes an alkylureido group, an arylureido group.
  • the sulfamoylamino group includes an alkylsulfamoylamino group, an arylsulfamoylamino group.
  • the heterocyclic group is preferably a to 7-member heterocyclic group such as a 2-furyl group, a 2-thienyl group, a 2-pyrimidinyl group, a 2-benzothiazolyl group.
  • the heterocyclic oxy group is preferably one having a 5 to 7-member heterocyclic ring, such as a 3,4,5,6-tetrahydropyranyl-2-oxy group, a I-phenyltetrazole-5-oxy group.
  • the heterocyclic thio group is preferably a 5 to 7-member heterocyclic thio group, such as a 2-pyridinylthio group, a 2-benzothiazolyl group, a 2,4-diphenoxy-1,3,5-triazola-6-thio group.
  • the siloxy group is preferably a trimethylsiloxy group, a triethylsiloxy group or a dimethylbutylsiloxy group.
  • the imido group is preferably a succinic acid imido group, a 3-heptadecylsuccinic acid imido group, a phthalimido group or a glutarimido group.
  • the spiro compound residue includes a spiro[3.3]heptane-1-yl group.
  • the bridged hydrocarbon compound residue includes a bicyclo[2.2.1]heptane-1-yl group, a tricyclo-[3.3.1.1 3.7 ]decane-1-yl group, a 7,7-dimethyl-bicyclo[2.2.1]heptane-1-yl group.
  • the substituent represented by X which is capable of being split off upon the reaction with the oxidation product of a color developing agent, is, e.g., a halogen atom such as chlorine, bromine, fluorine; or an alkoxy, aryloxy, heterocyclic oxy, acyloxy, sulfonyloxy, alkoxycarbonyloxy, aryloxycarbonyl, alkylox- alyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthio, acylamino, sulfonamido, nigrogen atom-bonded nitrogen-containing heterocyclic, alkyloxycarbonylamino, aryloxycarbonylamino or carboxyl group or a group having the formula: wherein R 1 ' is as defined for the foregoing R; Z is as defined for the foregoing Z; R2 and R 3 ' each represents a
  • halogen atom particularly a chlorine atom.
  • the nitrogen-containing heterocyclic ring represented by Z or Z' is a pyrazole ring, an imidazole ring, a triazole ring or a tetrazole ring, and the substituent which the above ring may have is as defined in the above R.
  • R 1 to R 8 and X are as defined for the foregoing R and X, respectively.
  • magenta couplers represented by Formulas II through VII are the magenta couplers having Formula II.
  • R g is a hydrogen atom or an alkyl group.
  • the alkylene group represented by R 1 is a straight-chain or branched-chain one whose straight-chain portion has preferably not less than 2 carbon atoms, and more preferably 3 to 6 carbon atoms.
  • the cycloalkyl group represented by R 2 is preferably a 5 or 6-member cycloalkyl group.
  • the Compounds according to the present invention also include the compounds Nos. 1 to 4, 6, 8 to 17, 19 to 43, 45 to 49, 61 to 104, 106 to 121, 123 to 162, and 164 to 223 out of those compounds disclosed in pages 66 to 122 of Japanese Patent Publication Open to Public Inspection (hereinafter referred to as Japanese Patent O.P.I. Publication) No. 166339/1987.
  • These coupler compounds can be synthesized by making reference to Perkin, the 'Journal of the Chemical Society', I (1977), 2047 through 2052; U.S. Patent No. 3,725,067; Japanese Patent O.P.I. Publication Nos. 99437/1984, 42045/1983, 162548/1984, 171956/1984, 33552/1985, 43659/1985, 172982/1985 and 190779/1985.
  • the coupler of the invention may be used in the amount range of 1x10 -3 mole to 1 mole, and preferably 1x10 -2 to 8x10 -1 mole per mole of silver halide.
  • the coupler of the invention may be used in combination with a different-tye coupler within the limits not to impair the effect of this invention.
  • the DIR compound herein implies a compound from which is split off a development inhibitor or a compound capable of releasing a development inhibitor upon the reaction with the oxidation product of a color developing agent.
  • the compound capable of releasing a development inhibitor may be either one releasing a development inhibitor imagewise or one releasing non-imagewise.
  • Y is typically represented by the following Formulas D-2 through D-20:
  • Rd 1 represents a hydrogen atom, a halogen atom,or an alkyl, alkoxy, acylamino, alkoxycarbonyl, thiazolidinylideneamino, aryloxycarbonyl, acyloxy, carbamoyl, N-alkylcarbamoyl, N,N-dialkylcarbamoyl, nitro.
  • n is an integer of 0, 1 or 2, provided that when n is 2, the Rd 1 s may be either the same or different, and total number of the carbon atoms contained in the n number of Rd 1 s are from zero up to 10.
  • the number of carbon atoms contained in the Rd 1 in Formula D-6 is zero to 15.
  • X represents an oxygen atom or a sulfur atom.
  • Rd 2 represents an alkyl group, an aryl group or a heterocyclic group.
  • Rd 3 represents a hydrogen atom or an alkyl, cycloalkyl, aryl or a heterocyclic group
  • Rd 4 is a hydrogen atom, a halogen atom or an alkyl, cycloalkyl, aryl, acylamino, alkoxycarbonylamino aryloxycarbonylamino, alkanesulfonamido, cyano, heterocyclic. alkylthio or amino group.
  • Rd 1 , Rd 2 , Rd 3 or Rd 4 represents an alkyl group
  • the alkyl group includes one having a substituent, and may be either straight-chain or branched-chain.
  • Rd 1 , Rd 2 , Rd 3 or Rd 4 represents an aryl group
  • the aryl group includes one having a substituent.
  • Rdi, Rd 2 , Rd 3 or Rd 4 represents a heterocyclic group
  • the heterocyclic group includes one having a substituent, wherein the heterocyclic group is preferably a 5- or 6-member single ring or condensed ring containing at least one hetero atom selected from the group consisting of nitrogen, oxygen and sulfur atoms.
  • the heterocyclic group is selected from among, e.g., pyridyl, quinolyl, furyl, benzothiazole, oxazol yl, imidazolyl, thiazolyl, triazolyl, benzotriazolyl, imido, and oxazine.
  • the number of carbon atoms contained in Rd 2 is from zero to 15.
  • Formula D-9 the total number of carbon atoms contained in Rd 3 and Rd 4 is from zero to 15.
  • Formula D-10 -(TIME) n -INHIBIT wherein TIME group is combined to the coupling position of A and is a group capable of being split off upon the reaction with the oxidation product of a color developing agent. After being split-off from the coupler, TIME groups are then in turn further cleaved to eventually moderately control and release an INHIBIT group; and n is an integer of 1 to 3, provided that when n is 2 or 3, the TIME groups may be either the same or different.
  • the INHIBIT group is a group represented by one of Formulas D-2 through D-9, which group becomes a development inhibitor due to the above-mentioned release.
  • TIME group is typified by ones represented by the following Formulas D-11 through D-19:
  • Rd s represents a hydrogen atom, a halogen atom, or an alkyl, cycloalkyl, alkenyl, aralkyl, alkoxy, alkoxycarbonyl anilino, acylamino ureido, cyano, nitro, sulfonamido, sulfamoyl, carbamoyl, aryl, carboxy, sulfo, hydroxy or alkanesulfonyl group, provided that in Formulas D-11 to D-13, D-15 and D-18, the Rdss may combine with one another to form a condensed ring.
  • Rd 6 is an alkyl, alkenyl, aralkyl, cycloalkyl, heterocyclic or aryl group.
  • Rd 7 is a hydrogen atom or an alkyl, alkenyl, aralkyl, cycloalkyl, heterocyclic or aryl group.
  • Rds and Rds each represents a hydrogen atom or an alkyl group having preferably 1 to 4 carbon atoms.
  • k is an integer of zero, 1 or 2; in Formulas D-11 through D-13, D-15 and D-18, 1 is an integer of 1 to 4; and in Formula D-16, m is an integer of 1 or 2.
  • R 5 s and Rd 7 s may be either the same or different, respectively.
  • n is an integer of 2 to 4.
  • the n Rd 8 s and n Rdgs may be independently the same or different.
  • B represents an oxygen atom or , wherein Rd 6 is as defined previously.
  • ---- may be either a single bond or double bonded and when it is a single bond, m is 2, while when it is a double bond, m is 1.
  • Formula D-20 ( ⁇ T 1 SR( ⁇ T 2 , INHIBIT wherein T, is a component which splits off the SR( ⁇ T 2 INHIBIT, wherein SR is a component which, after the SR( ⁇ T 2 , INHIBIT, is produced, produces a (T 2 INHIBIT by he reaction with the oxidation product of a developing agent, T 2 is a component which, after the (T 2 , INHIBIT is produced, splits off an INHIBIT, and INHIBIT is a development inhibitor; and 1 and m each is an integer of zero or 1.
  • the component represented by SR need only be one capable of forming the above component by the reaction with the oxidation product of a developing agent, and includes, e.g., a coupler component which effects coupling reaction with the oxidation product of a developing agent and a redox component which effects redox reaction with the oxidation product of a developing agent.
  • the coupler component includes yellow couplers, magenta couplers and cyan couplers, such as acylacetanilides, 5-pyrazolones, pyrazoloazoles, phenols, naphthols, acetophenones, indanones, cabamoylacetanilides, 2(5H)-imidazolones, 5-isooxazolones, uracils, homophthalimides, oxazolones, 2,5-thia diazoline-1,1-dioxides, triazolothiadiazines, indoles, and also includes other compounds capable of forming various dyes or compounds forming no dyes.
  • acylacetanilides such as acylacetanilides, 5-pyrazolones, pyrazoloazoles, phenols, naphthols, acetophenones, indanones, cabamoylacetanilides, 2(5H)-imidazolones,
  • the -(T 1 )-1 SR-(T 2 -m, INHIBIT preferably combines to the active site of the A component in Formula D1.
  • SR When SR is a coupler component, the SR combines with -(T 1 )-1 and -(T 2 )-m, INHIBIT so hat it functions as a coupler after being cleaved from the -(T 1 )-1.
  • the oxygen atom of its hydroxyl group when it is a 5-pyrazolone, the oxygen atom of the 5th-position hydroxyl group of or the 2nd-position nitrogen atom of its tautomer, or when it is an acetophenone or an indanone, the oxygen atom of the hydroxyl group of its tautomer preferably combines with the -(T 1 )-1 and the -(T 2 )-m, INHBIT preferably combines to the active site of the coupler.
  • SR is a redox component
  • examples of the redox component include hydroquinones, catechols, pyrogallols, aminophenols such as p-aminophenols and o-aminophenols, naphthalenediols such as 1,2-naphthalenediols, 1,4-naphthalenediols and 2,6-naphthalenediols, aminonaphthols such as 1,2-aminonaphthols, 1,4-aminonaphthols and 2.6-aminonaphthols.
  • the SR when SR is a redox component. the SR combines with -(T 1 )- and -(T 2 )-m, INHIBIT so that it functions as the redox component after being cleaved from the -(T 1 )-.
  • T, and T 2 include those represented by Formulas D-11 through D-19.
  • the development inhibitor represented by INHIBIT includes those represented by Formulas D-2 through D-9.
  • DIR compounds Preferred among the DIR compounds are.those of which the group of Y is represented by Formula D-2, D-3, D-8, D-10 or D-20. Among those with the groups Y represented by Formulas D-10 and D-20, the preferred are ones whose INHIBIT is represented by Formula D-2, D-3, D-6 (particularly when the X of Formula D-6 is an oxygen atom) or D-8.
  • the coupler component represented by A in Formula D-1 includes a yellow dye image forming coupler residue, a magenta dye image forming coupler residue, a cyan dye image forming coupler residue and a colorless coupler residue.
  • R 1 , T 2 and Y represent the following groups.
  • the DIR compound in the invention is used in an amount of preferably 0.0001 to 0.1 mole, more preferably 0.001 to 0.05 mole per mole of silver.
  • the DIR compound is preferably added in a layer where the compound can influence the development of silver halide in a single-layer-component emulsion layer, preferably a silver halide emulsion layer, and more preferably a single-layer-component silver halide emulsion layer.
  • the emulsion may be chemically sensitized in usual manner, and may also be optically sensitized to a desired wavelength region by using an appropriate sensitizing dye.
  • an antifoggant a stabilizer, etc. It is advantageous to use gelatin as the binder of the emulsion.
  • the emulsion layer and other hydrophilic colloid layers may be hardened, and may contain a plasticizer or a less-soluble synthetic polymer dispersion (latex).
  • Dye-forming couplers are used in the emulsion layers of the color photographic light-sensitive material of the invention.
  • color correction effect-having colored couplers may be used which, as a result of coupling with the oxidation product of a developing agent, release photographically useful fragments such as a developing agent, a silver halide solvent, a toning agent, a hardener, an antifoggant, a chemical sensitizer, a spectral sensitizer and a desensitizer.
  • the light-sensitive material may comprise auxiliary layers such as a filter layer, an antihalation layer, an antiirradiation layer and the like. These layers and/or emulsion layers may contain a dye which dissolves out of the light-sensitive material or is bleached in the course of processing.
  • a formalin scavenger a brightening agent, a matting agent, a lubricant, an image stabilizer, a surfactant, a color fog inhibitor, a developement accelerator, a development moderater and a bleaching accelerator.
  • polyethylene-laminated paper polyethylene terephthalate film, baryta paper, cellulose triacetate film or the like may be used.
  • the processing may be carried out by a generally known color photographic processing method after camera exposure.
  • the gelatin solution containing the total AgX grains was adjusted to pH5.5 with a potassium carbonate solution, and then to it were added 364 ml of a 5% aqueous solution of Demol N as a precipitant, a product of Kawo Atlas Co., and 244 ml of a 20% aqueous solution of magnesium sulfate as a polyvalent ion for coagulation, it was then allowed to stand for flocculation, and the supernatant was removed by decantation.
  • the obtained emulsion was regarded as NE-1.
  • the NE-1 when observed through an electron microscope, was a monodisperse emulsion comprising cubic grains having an average grain size of 0.093u.m.
  • seed emulsion NE-2 was prepared under the same conditions as in Preparation Example 1 except that the K 3 RhCl 6 was removed.
  • the emulsion was a monodisperse emulsion comprising cubic grains having an average grain size of 0.093u.m.
  • the seed emulsions prepared in Preparation Example 1 and the seven different solutions shown below were used to prepare core/shell-type monodisperse silver iodobromide emulsions Em-1 and Em-2 each having an average grain size of 0.4 ⁇ m and an average Agl content of 8 mole% in compositions comprising 15 mole%, 5 mole% and 3 mole% Agl contents in order from the inside core of the grain.
  • coated weights of the silver halide and colloidal silver are given in silver equivalent amounts in g/m 2
  • those of the additives and gelatin are given in g/m 2
  • those of the sensitizing dyes, couplers and DIR compounds are given in molar amounts per mole of silver halide in the following table.
  • the emulsions contained in the respective color-sensitive emulsion layers are ones optimally chemically sensitized by sodium thiosulfate and chloroauric acid.
  • Comparative coupler A (conventional coupler)
  • Each sample was divided into two parts; one part was allowed to stand for 3 days in a desiccator of which the inside atmosphere was kept at 35' C and a relative humidity of 65% by an aqueous solution containing 4 ml of 50-fold diluted formalin, into which a saturated amount of cobalt chloride was dissolved, and the other part was allowed to stand likewise in a desiccator conditioned in quite the same way except that the formalin was excluded (for comparative standing).
  • Formaline resistance the density of one part that was allowed to stand under the formaline condition by an exposure amount that gives a density of 1.0 of the other part under the comparative standing condition.
  • the formalin resistance improving effect when a magenta coupler of the invention is used is about two or three times larger than that when a comparative coupler was used, whereas where the green-sensitive layer of the invention is of a single-layer construction, the formaling resistance improving effect is as significantly improved as 6 times to 9 times larger.
  • the preservability of the samples Nos.106 through 109 is significantly improved.
  • the improving effect is one totally beyond our expectation from both the improving effect of the green-sensitive layer and that of the coupler of the invention.
  • the samples for the invention since its green- sensitive layer is of a single layer construction, is excellent in the sharpness as well as in the processing stability.
  • the silver halide color photographic light-sensitive material that satisfies the construction requirements of the invention is significantly improved in the formalin resistance and excellent in the preservability.
  • the sample prepared in the same manner as in sample No.106 for the invention except that the Em-2 in the G-1 of sample No.106 was replaced by an equimolar mixture of emulsions Em-2 and Em-A is preferably because it has an exposure latitude 40% wider than that of sample No.106.
  • the sample prepared in the same manner as in the above sample except that the Em-2 and Em-A contained in the above sample were replaced by an emulsion prepared by mixing Em-1 and Em-2 in a molar ratio of 3:7 is so improved in the processing stability that it has a 50% less change in the sensitivity due to the change in pH of the processing solution.
  • an emulsion partially comprising silver halide grains containing a desensitizer in the inside thereof for the light-sensitive layer of a single layer construction makes possible not only to obtain a wide exposure latitude in spite of the small coefficient of variation of the grain size of the silver halide contained in the light-sensitive layer but also to improve the processing stability, thus being a preferred embodiment of the present invention.
  • sample having blue-sensitive and green-sensitive layers each being of a single-layer construction prepared in the Same manner as in sample No.106 except that the B-2 of sample No.106 is removed and the Em-2 contained in the B-1 is replaced by an emulsion in an equimolar mixture of Em-2 and Em-A, and the sample having blue-sensitive and green-sensitive layers each being of a single-layer construction prepared in the same manner except that the Em-2 and Em-A mentioned above were replaced by an emulsion prepared by mixing Em-1 and Em-2 in a molar ratio of 3:7 are also found to have the same tendency as the above with respect to the exposure latitude and processing stability, and at the same time, to have even more improved sharpness.
  • a silver idodobromide emulsion having an average Agl content of 8.5 mole% and an average grain size of 0.7 ⁇ rn was prepared in making reference to the foregoing preparation method, in which the Agl content is higher in the inside of the grain and seed emulsion is NE-1.
  • the obtained emulsion was regarded as Em-B.
  • Sample No.201 was prepared in the same manner as in sample No.101 in Example 1.
  • Sample No.202 was prepared in the same manner as in sample No.201 except that the G-2 was removed and the Em-2 contained in the G-1 of sample No.201 was replaced by an equimolar mixture of emulsions Em-2 and Em-A.
  • Sample No.203 was prepared in the same manner as in sample No.201 except that the G-2 was removed and the Em-2 contained in the G-1 of sample No.201 was replaced by an equimolar mixture of emulsions Em-A and Em-B.
  • the obtained sample was exposed and processed in the same manner as in Example 1. Subsequently, the preservability with time and the exposure latitude were evaluated. The results are listed in Table 6.
  • Sample No.301 was prepared in the same manner as in sample No.101 in Example 1 except that the R-2 and B-2 were removed and the Em-2 contained in the R-1 was replaced by an equimolar mixture of emulsions Em-A and Em-2, and the Em-2 contained in the B-1 was replaced by an equimolar mixture of emulsions Em-A and Em-2.
  • Sample No.302 was prepared in the same manner as in sample No.301 except that the G-2 was removed and the Em-2 contained in the G-1 of sample No.301 was replaced by an equimolar mixture of emulsions Em-2 and Em-A.
  • Sample No.303 was prepared in the same manner as in sample No.301 except that the G-2 was removed and the Em-2 contained in the G-1 of sample No.301 was replaced by an equimolar mixture of emulsions Em-A and Em-B.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
EP19890310584 1988-10-15 1989-10-16 A silver halide color photographic light-sensitive material for making color negatives Withdrawn EP0365252A3 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP259855/88 1988-10-15
JP25985588A JPH02106743A (ja) 1988-10-15 1988-10-15 ハロゲン化銀カラー写真感光材料

Publications (2)

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EP0365252A2 true EP0365252A2 (fr) 1990-04-25
EP0365252A3 EP0365252A3 (en) 1990-11-14

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EP19890310584 Withdrawn EP0365252A3 (en) 1988-10-15 1989-10-16 A silver halide color photographic light-sensitive material for making color negatives

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EP (1) EP0365252A3 (fr)
JP (1) JPH02106743A (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0661591A2 (fr) 1993-12-29 1995-07-05 Eastman Kodak Company Eléments photographiques contenant un latex de polymère changé absorbant l'ultraviolet
EP0695968A2 (fr) 1994-08-01 1996-02-07 Eastman Kodak Company Réduction de la viscosité dans une composition photographique à l'état fondue

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2708466A1 (de) * 1977-02-26 1978-08-31 Agfa Gevaert Ag Emulsionsabmischungen fuer colorumkehr-(aufsichts-)material
JPH0746215B2 (ja) * 1985-05-01 1995-05-17 コニカ株式会社 ハロゲン化銀写真感光材料
JPS625234A (ja) * 1985-07-01 1987-01-12 Fuji Photo Film Co Ltd ハロゲン化銀カラ−写真感光材料
JPS62151850A (ja) * 1985-12-26 1987-07-06 Fuji Photo Film Co Ltd ハロゲン化銀カラ−写真感光材料

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0661591A2 (fr) 1993-12-29 1995-07-05 Eastman Kodak Company Eléments photographiques contenant un latex de polymère changé absorbant l'ultraviolet
EP0695968A2 (fr) 1994-08-01 1996-02-07 Eastman Kodak Company Réduction de la viscosité dans une composition photographique à l'état fondue

Also Published As

Publication number Publication date
EP0365252A3 (en) 1990-11-14
JPH02106743A (ja) 1990-04-18

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