EP0486216B1 - Photographisches lichtempfindliches Silberhalogenidmaterial - Google Patents

Photographisches lichtempfindliches Silberhalogenidmaterial Download PDF

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Publication number
EP0486216B1
EP0486216B1 EP91310285A EP91310285A EP0486216B1 EP 0486216 B1 EP0486216 B1 EP 0486216B1 EP 91310285 A EP91310285 A EP 91310285A EP 91310285 A EP91310285 A EP 91310285A EP 0486216 B1 EP0486216 B1 EP 0486216B1
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Prior art keywords
group
formula
silver halide
light
represented
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French (fr)
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EP0486216A1 (de
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Motoi Nishimura
Hirokazu Sato
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Konica Minolta Inc
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Konica Minolta Inc
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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
    • G03C7/392—Additives
    • G03C7/39208—Organic compounds

Definitions

  • the present invention relates to a light-sensitive silver halide photographic material. More particularly, it relates to a light-sensitive silver halide photographic material that can form a dye image having been improved in fastness to light and also having been prevented from being stained.
  • Dye images obtained using light-sensitive silver halide photographic materials are desired not to undergo discoloration or fading even after they have been subject to light for a long time or stored in an environment of high temperature and high humidity. They are also desired to be free from yellowing (hereinafter “Y-stain”) that may occur at their non-image portions because of light, humidity or heat.
  • a metal complex having a singlet oxygen quenching rate constant kq of not less than 3 x 10 7 M -1 s -1 is used to improve the fastness to light of dye images, as disclosed in Japanese Patent Publications Open to Public Inspection (hereinafter referred to as "Japanese Patent O.P.I. Publication(s)") No. 262740/1986, No. 267049/1986, No. 175754/1987, No. 187348/1987, No. 182741/1987, No. 183459/1987, etc.
  • Japanese Patent O.P.I. Publication No. 958/1990 also discloses that the storage stability can be improved when a compound with kq of not less than 1 x 10 7 M -1 s -1 is made present in a heat-developable color light-sensitive element having a dye-providing compound capable of forming or releasing a diffusible dye, corresponding or reverse corresponding with the reaction in which a light-sensitive silver halide, a binder and a silver halide are reduced to silver.
  • Sole use of the compound having the above kq can not be said to be satisfactory for preventing the fading and discoloration of color images against light.
  • Such pyrazoloazole magenta couplers have been advantageous in that the Y-stain at the non-image portions may hardly occur against light, heat and humidity, but on the other hand disadvantageous in that the azomethin dye formed has a very low fastness to light and also tends to undergo the discoloration by light, to seriously damage the performances of, in particular, light-sensitive color photographic materials for printing. No satisfactory effect has been obtainable even when the compound having the above kq is solely used together with any of these couplers.
  • Japanese Patent O.P.I. Publication No. 3995/1991 discloses a technique by which the fastness to light is improved and the Y-stain due to light, humidity and heat is prevented from occurring, by using a pyrazoloazole coupler in combination with an amine compound and a phenol compound. Nevertheless, no satisfactory effect of preventing fading for a long period of time was found to be obtained even by this method.
  • a first object of the present invention is to provide a light-sensitive silver halide photographic material that can form a dye image causing less discoloration against light.
  • a second object of the present invention is to provide a light-sensitive material that has prevented the Y-stain at the non-image portions from occurring against light, heat and humidity.
  • a third object of the present invention is to provide a light-sensitive material that is free from the secondary absorption of magenta dyes and has been improved in color reproduction quality.
  • a light-sensitive silver halide photographic material comprising a support carrying a silver halide emulsion layer containing a dye forming coupler, characterised in that the silver halide emulsion layer contains a compound having a singlet oxygen-quenching ability with a quenching rate constant Kq of not less than 1 X 10 8 M -1 s -1 and having the Formula II-a-2; wherein Y' is a group of non-metallo atoms necessary to complete a heterocyclic ring having from 5 to 8 members; R 10 is an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group.
  • R 11 and R 13 are each an electron donating group having a Hammett's ⁇ p value of not more than 0; and R 12 and R 14 are each hydrogen atoms; and a compound represented by the Formula R; wherein R 15 is a substituent and l is an integer in the range 0 to 5; provided that the value of Kq is determined as follows: singlet oxygen is produced from 3-(1,4-epidioxyl-4-methyl-1,4-dihydro-1-naphthyl)proprionic acid in ethanol as solvent at 35 C; 2,5-diphenyl-3,4-benzofuran (DPBF), as a standard substance for quenching, is made present together with the substance to be measured; then both the substances are brought into competitive reaction with the singlet oxygen the changes with time of light absorption at the absorption wavelength of the DPBF ( ⁇ max: 411 nm) are
  • the present invention can be particularly effective when the dye forming coupler comprises a couple represented by the following Formula M-I
  • Z represents a group of non-metal atoms necessary to complete a nitrogen-containing heterocyclic ring.
  • the ring formed by X may have a substituent.
  • X represents a hydrogen atom or a group capable of being split off upon reaction with an oxidized product of a color developing agent.
  • R represents a hydrogen atom or a substituent.
  • the kq is determined by the measurement according to the method disclosed in Daifuku, Mukai et al., Ehime University, the Faculty of Science, SUMMARY COLLECTIONS OF THE 22ND OXIDATION FORUM, page 7.
  • singlet oxygen is produced from 3-(1,4-epidioxyl-4-methyl-1,4-dihydro-1-naphthyl)propionic acid (EP) in an ethanol solvent at 35°C according to the Inoue et al's Method disclosed in Tetrahedron Letter, 41, pp.2177-2181 (1985).
  • DPBF 2,5-diphenyl-3,4-benzofuran
  • a substance to be measured is made present together with this substance. Both the substances are brought into competitive reaction with the singlet oxygen, and changes with time of light absorbance at the absorption wavelength ( ⁇ max: 411 nm) of the DPBF are followed up to determine the kq.
  • Y' represents a group of non-metallo atoms necessary to complete a heterocyclic ring having from 5 to 8 members
  • R 10 represents an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, a bridged hydrocarbon group, an alkylsulfonyl group or an arylsulfonyl group.
  • R 11 to R 14 each represent an electron donative group having a Hammett's ⁇ p value of not more than 0.
  • the alkyl group represented by R 10 may preferably be a straight-chain or branched alkyl group having 1 to 24 carbon atoms, as exemplified by groups such as methyl, ethyl, isopropyl, t-butyl, 2-ethylhexyl, dodecyl, t-octyl and benzyl.
  • the cycloalkyl group may preferably be a cycloalkyl group having 5 to 24 carbon atoms, as exemplified by groups such as cyclopentyl and cyclohexyl.
  • the alkenyl group may preferably be an alkenyl group having 3 to 24 carbon atoms, as exemplified by groups such as aryl and 2,4-pentadienyl.
  • the aryl group may include, for example, groups such as phenyl and naphthyl.
  • the heterocyclic group may include, for example, groups such as pyridyl, imidazolyl and thiazolyl.
  • the acyl group may include, for example, groups such as acetyl and benzoyl.
  • the bridged hydrocarbon group may include, for example, groups such as bicyclo[2.2.1]heptyl.
  • the alkylsulfonyl group may include, for example, groups such as dodecylsulfonyl and headecylsulfonyl.
  • the arylsulfonyl group may include, for example, groups such as phenylsulfonyl.
  • the substituent of the alkyl group may include a halogen atom and groups such as hydroxyl, alkoxyl, aryl, acylamino, sulfonamide, aryloxy, alkylthio, carbamoyl, sulfamoyl, alkylsulfonyl, nitro, cyano, arylsulfonyl, carboxyl, amino, arylamino, alkylamino, alkoxycarbonayl, acyl and acyloxy.
  • the substituent of the group represented by R 10 except for the alkyl group may include the substituents described above and an alkyl group.
  • R 10 preferably represents an alkyl group.
  • R 11 to R 14 each represent an electron donative group having a Hammett's ⁇ p value of not more than 0.
  • R 12 and R 14 each represent a hydrogen atom.
  • the kq of the compound having a singlet oxygen quenching rate constant kq of not less than 1 x 10 8 M -1 s -1 may preferably be within the range of from 1 x 10 8 M -1 s -1 to 1 x 10 9 M -1 s -1 .
  • the compound having a radical-scavenging ability may preferably be a compound having a radical-scavenging rate constant Ks of 10 -1 to 2 x 10 4 M -1 s -1 .
  • PhO ⁇ 2,6-di-t-butyl-4-(4'-methoxyphenyl)phenoxyl radical
  • the quenching compound having the above ks of 10 -1 to 2 x 10 4 M -1 s -1 has the structure of the following Formula R.
  • R 15 represents a substituent that can be substituted on the benzene ring
  • l represents an integer of 0 to 5.
  • a plurality of R 15 may be the same or different one another, and R 15 's may mutually combine to form a ring.
  • the group represented by R 15 in Formula R may preferably include an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an acylamino group, a sulfonamide group, an alkylamino group, an alkylthio group, an arylthio group, an alkoxycarbonyl group, an aryloxycarbonyl group, a halogen atom and a group -OR 16 .
  • R 16 represents an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a heterocyclic group or a group wherein R 16a , R 16b and R 16c may be the same or different one another, and each represent an alkyl group, an alkenyl group, an aryl group, an alkoxyl group, an alkenoxy group or an aryloxy group.
  • the alkyl group represented by R 15 may include a straight-chain or branched alkyl group having 1 to 24 carbon atoms as exemplified by groups such as methyl, ethyl, i-propyl, t-butyl, octyl, 2-ethylhexyl, dodecyl, tetradecyl, hexadecyl, eicocyl and benzyl.
  • the cycloalkyl group represented by R 15 may include a cycloalkyl group having 5 to 24 carbon atoms as exemplified by groups such as cyclopentyl and cyclohexyl.
  • the alkenyl group may include an alkenyl group having 2 to 24 carbon atoms as exemplified by groups such as ethenyl, propenyl, butenyl, octenyl, decenyl and oleyl.
  • the aryl group represented by R 15 may include a phenyl group and a naphthyl group.
  • the halogen atom may include, for example, atoms such as fluorine, chlorine, bromine and iodine.
  • the acylamino group may include, for example, groups such as acetylamino and benzoylamino.
  • the sulfonamide group may include, for example, groups such as methylsulfonylamino and benzenesulfonylamino.
  • the alkyl component that constitutes the alkylamino group and alkylthio group may include the same as those of the alkyl group previously described.
  • the aryl component that constitutes the arylthio group may include the same as those of the aryl group previously described.
  • the alkoxycarbonyl group may include, for example, groups such as methoxycarbonyl, ethoxycarbonyl, benzyloxycarbonyl.
  • the aryloxycarbonyl group may include, for example, a phenoxycarbonyl group.
  • the alkyl group, the cycloalkyl group, the aryl group or the heterocyclic group, or a group having any of these groups even in part, may further has a substituent.
  • the substituent for the alkyl group or cycloalkyl group may include a halogen atom and groups such as hydroxyl, alkoxyl, alkylthio, acylamino, sulfonamide, aryl, aryloxy, carboxyl, amino, alkylamino, arylamino, carbamoyl, sulfamoyl, alkylsulfonyl, arylsulfonyl, nitro, cyano, alkoxycarbonyl, acyl and acyloxy.
  • groups such as hydroxyl, alkoxyl, alkylthio, acylamino, sulfonamide, aryl, aryloxy, carboxyl, amino, alkylamino, arylamino, carbamoyl, sulfamoyl, alkylsulfonyl, arylsulfonyl, nitro, cyano, alkoxycarbonyl, acy
  • the substituents other than the alkyl group may include the substituents set forth above and an alkyl group.
  • the substitutents the aryl group and heterocyclic group may have may include a halogen atom and groups such as alkyl, aryl, alkoxyl, aryloxy, alkylthio, arylthio, acyl, acylamino, sulfonamide, carbamoyl, sulfamoyl, ureido, alkoxycarbonyl, amino, sulfonyl, nitro, cyano and carboxyl.
  • a halogen atom and groups such as alkyl, aryl, alkoxyl, aryloxy, alkylthio, arylthio, acyl, acylamino, sulfonamide, carbamoyl, sulfamoyl, ureido, alkoxycarbonyl, amino, sulfonyl, nitro, cyano and carboxyl.
  • the ring that may be formed by any mutual combination of a plurality of R 15 may include an indane ring, a cumarane ring, a naphthalene ring and a chromane ring.
  • the spiro ring may include a spirobiindane ring, a spirobicumaran ring and a spirobichroman group.
  • R 15 is a hydroxyl group
  • the compound represented by Formula R is not preferable because of its properties that it reacts with an oxidized product of a developing agent to inhibit the dye formation of the dye forming coupler.
  • R 15 and R 15' each have the same definition for R 15 in Formula R, and A represents a divalent connecting group.
  • Letter symbols a and a' each represent an integer of 0 to 4. In the case when a or a' is two or more, a plurality of R 15 or R 15' may be the same or different one another. R 15 and R 15' may also combine to form a ring.
  • R 15' and R 15" each have the same definition for R 15 in Formula R, and may be the same or different each other.
  • Letter symbols b and b' each represent an integer of 0 to 3. In the case when b or b' is two or more, a plurality of R 15' or R 15" may be the same or different one another, and may also combine to form a ring.
  • R 15 and R 15' may be the same or different each other, and each have the same definition for R 15 in Formula R.
  • Letter symbols a' and a" each represent an integer of 0 to 4.
  • the letter symbol A represents a divalent connecting group.
  • R 16 , R 16' , a', a" and A have the same definitions for R 16 , R 16' , a', a" and A, respectively, in Formula R-a-1.
  • R 16 and R 16' may include the groups detailed for R 15 in Formula R.
  • the A represents a divalent connecting group, as exemplified by an alkylene group, etc. wherein R 17 represents a hydrogen atom or a substituted or unsubstituted alkyl group or phenyl group in all instances.
  • the alkylene group may have a single or plural number of substituent(s).
  • substituent(s) may include, for example, an aryl group, a cyano group, a halogen atom, a heterocyclic group, a cycloalkyl group, an alkoxyl group, a hydroxyl group and an aryloxy group.
  • This alkylene group may also be those in which the alkylene chain itself constitutes a cycloalkyl ring, as in the following:
  • the A may also include those in which the above divalent connecting groups are arbitrarily connected in plurality.
  • particularly preferred compounds may include structures represented by Formula R-b-1 or R-b-2.
  • R 15 , R 15' , b and b' have the same definitions for R 15 , R 15' , b and b', respectively, in R 18 , R 18' , R 19 and R 19' each represent a hydrogen atom, a substituted or unsubstituted aliphatic group, a substituted or unsubstituted aromatic group or a substituted or unsubstituted heterocyclic group.
  • R 15' , R 15" , b, b' and D have the same definitions for R 15' , R 15" , b, b' and D, respectively, in Formula R-b-1.
  • the compound having a radical-scavenging ability is not the same as the compound having a singlet oxygen quenching rate constant kq of not less than 1 x 10 8 M -1 s -1 .
  • the compound having a radical-scavenging ability may preferably have a radical-scavenging rate constant Ks in the range of from 10 -1 M -1 s -1 to 2 x 10 4 M -1 s -1 , and more preferably from 10 -1 M -1 s -1 to 10 3 M -1 s -1 .
  • Z represents a group of non-metal atoms necessary to complete a nitrogen-containing heterocyclic ring.
  • the ring formed by said Z may have a substitutent.
  • X represents a hydrogen atom or a group capable of being split off upon reaction with an oxidized product of a color developing agent.
  • R represents a hydrogen atom or a substituent. There are no particular limitations on the substituent represented by R. It may typically include groups such as alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl and cycloalkyl.
  • halogen atom groups such as cycloalkenyl, alkynyl, a heterocyclic ring, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocyclic oxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imido, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl and heterocyclic thio, a spiro compound residual group, and a bridged hydrocarbon compound residual group.
  • a halogen atom groups such as cycloalkenyl, alkynyl, a heterocyclic ring, sulfonyl, sulfinyl, phosphonyl,
  • the alkyl group represented by R may preferably include those having 1 to 32 carbon atoms, which may be either straight-chain or branched.
  • the aryl group represented by R may preferably include a phenyl group.
  • the acylamino group represented by R may include an alkylcarbonylamino group and an arylcarbonylamino group.
  • the sulfonamide group represented by R may include an alkylsulfonylamino group and an arylsulfonylamino group.
  • the alkyl component or aryl component in the alkylthio group or arylthio group represented by R may include the alkyl group or aryl group represented by R.
  • the alkenyl group represented by R may preferably include those having 2 to 32 carbon atoms; and the cycloalkyl group, those having 3 to 12 carbon atoms, and particularly 5 to 7 carbon atoms.
  • the alkenyl group may be either straight-chain or branched.
  • the cycloalkenyl group represented by R may preferably include those having 3 to 12 carbon atoms, and particularly preferably 5 to 7 carbon atoms.
  • the sulfonyl group represented by R may include an alkylsulfonyl group and an arylsulfonyl group;
  • the group represented by X capable of being split off through the reaction with an oxidized product of a color developing agent, may include, for example, a halogen atom such as a chlorine atom, a bromine atom or a fluorine atom, and groups such as alkoxy, aryloxy, heterocyclic oxy, acyloxy, sulfonyloxy, alkoxycarbonyloxy, aryloxycarbonyl, alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthio, acylamino, sulfonamido, a nitrogen-containing heterocyclic ring bonded with a N atom, alkyloxycarbonylamino, aryloxycarbonylamino, carboxyl, and wherein R 1 ' has the same definition for the above R, and Z', the same definition for the above Z; and R 2 ' and R
  • the nitrogen-containing heterocyclic group formed by Z or Z' may include a pyrazole ring, an imidazole ring, a triazole ring or a tetrazole ring, and the substituent the above ring may have may include those described for the above R.
  • the coupler represented by Formula M-I is more specifically represented, for example, by the following Formulas M-II to M-VII.
  • R 1 to R 8 and X have the same definitions for the above R and X, respectively.
  • Formula M-I preferred is the one represented by Formula M-VIII shown below.
  • R 1 , X and Z 1 have the same definitions for R, X and Z, respectively, in Formula M-I.
  • magenta couplers represented by Formulas M-II to M-VII particularly preferred magenta couplers are the magenta couplers represented respectively by Formulas M-II and M-III.
  • R 1 is the substituent of Formula M-IX.
  • R 9 , R 10 and R 11 each have the same definitions for the above R.
  • R 9 , R 10 and R 11 may also combine to form a saturated or unsaturated ring as exemplified by cycloalkane, cycloalkene and a heterocyclic ring, and the ring thus formed and R 11 may further combine to form a bridged hydrocarbon compound residual group.
  • R 9 to R 11 are alkyl groups
  • R 9 to R 11 is a hydrogen atom
  • R 9 and R 10 combine to form cycloalkyl together with the route carbon atom
  • R 2 to R 8 in Formulas M-II to M-VI may preferably include those represented by Formula M-X shown below.
  • R 12 represents an alkylene group
  • R 13 represents an alkyl group, a cycloalkyl group or an aryl group.
  • the alkylene group represented by R 12 may preferably have two or more, more preferably 3 to 6, carbon atoms at the straight-chain moiety, and may be straight-chain or branched.
  • examples of the compounds which can be used in the present invention may also be the compounds shown as Nos. 1 to 4, 6, 8 to 17, 19 to 24, 26 to 43, 45 to 59, 61 to 104, 106 to 121, 123 to 162 and 164 to 223 among the compounds disclosed in Japanese Patent O.P.I. Publication No. 166339/1987, pages 66 to 122.
  • magenta coupler represented by the above Formula M-I can be readily synthesized by those skilled in the art, by making reference to Journal of the Chemical Society, Perkin I (1977), 2047-2052, U.S. Patent No. 3,725,067, Japanese Patent O.P.I. Publications No. 99437/1984, No. 42045/1983, No. 162548/1984, No. 171956/1984, No. 33552/1985, No. 43659/1985, No. 172982/1985 and No. 190779/1985, etc.
  • magenta couplers can be used usually in the range of from 1 x 10 -3 mol to 1 mol, and preferably from 1 x 10 -2 mol to 8 x 10 -1 mol, per mol of silver halide.
  • couplers can also be used in combination with magenta couplers of different types.
  • the compound having a singlet oxygen quenching rate constant kq of not less than 10 8 M -1 s -1 and the compound having a radical-scavenging ability may each preferably be used in an amount of from 5 mol % to 400 mol %, and more preferably from 10 mol % to 250 mol %.
  • the compound having kq of not less than 10 8 M -1 s -1 and the compound having a radical-scavenging ability may be used in their total amount of from 10 mol % to 500 mol %, and more preferably from 20 mol % to 400 mol %, based on the magenta coupler represented by Formuia M-I.
  • the compound having kq of not less than 10 8 M -1 s -1 and the compound having a radical-scavenging ability, according to the present invention, may preferably be used in a proportion of from 0.1 to 10, and more preferably in the range of from 0.25 to 4.0, in molar ratio of the former to the latter.
  • magenta coupler represented by Formula M-I the compound having kq of not less than 10 8 M s -1 s -1 and the compound having a radical-scavenging ability (serving as stabilizing agents) are used in the same layer. They may also be used in such a way that the stabilizing agents are used in a layer adjoining to the layer in which the coupler is present.
  • magenta coupler represented by Formula M-I the compound having kq of not less than 10 8 M -1 s -1 and the compound having a radical-scavenging ability, according to the present invention can be added to the light-sensitive material by various methods such as the solid-state dispersion, the latex dispersion and the oil-in-water emulsification dispersion.
  • hydrophobic additives such as the magenta coupler may usually be dissolved in a high-boiling organic solvent having a boiling point of 150°C or more or a water-insoluble polymeric compound, optionally together with a low-boiling and/or water-soluble organic solvent to effect emulsification dispersion in a hydrophilic binder such as an aqueous gelatin solution using a surface active agent, and thereafter the resulting emulsion may be added to the intended hydrophilic colloid layer.
  • a hydrophilic binder such as an aqueous gelatin solution using a surface active agent
  • the light-sensitive material of the present invention can be applied to, for example, color negative and positive films and color photographic papers.
  • the present invention can be remarkably effective particularly when applied to color photographic papers used for direct viewing.
  • the silver halide used in the present invention may include any silver halides such as silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide and silver chloroiodide.
  • Silver halide grains preferably used in the present invention may preferably have a silver chloride content of not less than 90 mol %, a silver bromide content of not more than 10 mol % and a silver iodide content of not more than 0.5 mol %. They may more preferably be silver chlorobromide grains having a silver bromide content of from 0.1 mol % to 2 mol %.
  • the silver halide grains may be used alone, or may also be used in combination with other silver halide grains having different composition. They may also be used in combination with silver halide grains having a silver chloride content of not more than 90 mol %.
  • the silver halide grains having a silver chloride content of not less than 90 mol % are held in a proportion of not less than 60 % by weight, and preferably not less than 80 % by weight, in the whole silver halide grains contained in the emulsion layer.
  • composition of silver halide grains may be uniform throughout a grain, from its inside to its outer portion, or may be different between the inside and outer portion of a grain. In the case when the composition of the grain is different between the inside and the outer portion, the composition may change continuously or discontinuously.
  • the grain size of the silver halide grains according to the present invention may be preferably in the range of from 0.2 ⁇ m to 1.6 ⁇ m, and more preferably from 0.25 ⁇ m to 1.2 ⁇ m.
  • the above grain size can be measured by various methods generally used in the present technical field. Typical methods are described in Loveland, "Grain Size Analytical Methods", A.S.T.M. Symposium on Light Microscopy, 1955, pp.94-122, or Mees and James, “The Theory of The Photographic Process", 3rd Ed., 2nd Chapter, Macmillan Publishing Co., Inc. (1966).
  • This grain size can be measured by use of the projected area or diameter approximate value of a grain. If the grains are of substantially uniform shape, the grain size distribution can be represented fairly accurately as the diameter or projected area.
  • the grain size distribution of the silver halide grains according to the present invention may be polydisperse or monodisperse. Prefered are monodisperse silver halide grains wherein, in the grain size distribution of the silver halide grains, its coefficient of variation is 0.22 or less, and preferably 0.15 or less.
  • ri represents the grain size of the individual grains; and ni, its number.
  • the grain size herein mentioned indicates the diameter when a silver halide grain is spherical; and, when it is cubic or of the form other than the spherical, the diameter obtained by calculating a projected image thereof as a round image having the same area.
  • the silver halide grains used in emulsions may be those obtained by any of the acid method, the neutral method and the ammoniacal method.
  • the grains may be grown at one time, or may be grown after making seed grains.
  • the method of making seed grains and the method of growing them may be the same or different.
  • the manner by which soluble silver salts are reacted with readily soluble halogen salts may be any of those including the normal precipitation, the reverse precipitation, the double-jet precipitation, and the combination of any of these. Preferred are grains obtained by the double-jet precipitation.
  • As one manner of the double-jet precipitation it is also possible to use the pAg-controlled double-jet precipitation described in Japanese Patent O.P.I. Publication No. 48521/1979.
  • a silver halide solvent such as thioethers may also be used.
  • a mercapto group-containing compound, a nitrogen-containing heterocyclic compound or a compound like a spectral sensitizer may also be used by adding them at the time the silver halide grains are formed or after the formation of grains has been completed.
  • silver halide grains used in the present invention those of any shape can be used.
  • a preferable example thereof is a cube having ⁇ 100 ⁇ face as a crystal surface.
  • the silver halide grains used in the present invention may be comprised of grains having a single shape, or comprised of a mixture of grains having various shapes.
  • metal ions may be added using a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or a complex salt thereof, in the course the grains are formed and/or in the course they are grown, whereby they can be incorporated in the insides of the grains and/or the surfaces thereof.
  • the silver halide grains may be placed in a reducing atmosphere, whereby reduction sensitization nuclei can be imparted to the insides of the grains and/or the surfaces of the grains.
  • excess soluble salts may be removed after the growth of the silver halide grains has been completed, or they may remain unremoved. In the case when the slats are removed, they can be removed by the method described in Research Disclosure No. 17643.
  • the silver halide grains used in emulsions may be those in which a latent image is mainly formed on the surfaces, or those in which it is formed in the insides of grains. It is preferred to use grains in which the latent image is mainly formed on the surfaces.
  • the emulsions are chemically sensitized by conventional methods. More specifically, the sulfur sensitization making use of a compound containing sulfur capable of reacting with silver ions or an active gelatin, the selenium sensitization making use of a selenium compound, the reduction sensitization making use of a reducing substance and the noble metal sensitization making use of a compound of noble metal such as gold or the like can be used alone or in combination.
  • the emulsions can also be spectrally sensitized to the desired wavelength region, using a spectral sensitizer.
  • the spectral sensitizer that can be used may include cyanine dyes, merocyanine dyes, composite cyanine dyes, composite merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxanol dyes.
  • the dye forming couplers used in the light-sensitive silver halide photographic material of the present invention are usually so selected that the dye capable of absorbing spectrum light to which an emulsion layer is sensitive is formed with respect to each emulsion layer.
  • a yellow dye forming coupler is used in a blue-sensitive emulsion layer
  • a magenta dye forming coupler in a green-sensitive emulsion layer and a cyan dye forming coupler in a red-sensitive emulsion layer.
  • the light-sensitive silver halide photographic material may be prepared by a method in which the couplers are used in the manner different from the above combination.
  • acylacetoanilide couplers can be preferably used as the yellow dye forming coupler.
  • benzoyl acetanilide compounds and pivaroyl acetanilide compounds are advantageous, and those particularly preferably usable are the exemplary compounds Y-1 to Y-146 disclosed in Japanese Patent O.P.I. Publication No. 85631/1988, the exemplary compounds Y-1 to Y-98 disclosed in Japanese Patent O.P.I. Publication No. 97951/1988, the exemplary compounds I-1 to I-50 disclosed in Japanese Patent O.P.I. Publication No. 298943/1990, and the exemplary compounds Y-1 to Y-24 disclosed in Japanese Patent Application No. 316996/1987.
  • magenta coupler represented by Formula M-I in addition to the magenta coupler represented by Formula M-I previously set forth, a magenta coupler represented by the following Formula M-II may also be used in combination.
  • Ar represents an aryl group
  • X represents a halogen atom, an alkoxyl group or an alkyl group
  • R represents a group capable of being substituted on the benzene ring.
  • the letter symbol n represents 1 or 2. In the case when n is 2, the groups R's may be the same or different.
  • Y represents a group capable of being split off upon reaction with an oxidized product of an aromatic primary amine color developing agent.
  • the group represented by Y capable of being split off upon reaction with an oxidized product of an aromatic primary amine color developing agent may include, for example, a halogen atom, an alkoxyl group, an aryloxy group, an acyloxy group, an arylthio group, an alkylthio group, and -N Z' wherein Z' represents a group of atoms necessary to complete a ring of 5 or 6 members formed by an atom selected from a carbon atom, an oxygen atom, a nitrogen atom and a sulfur atom, together with the nitrogen atom.
  • Y does not represent a hydrogen atom.
  • Halogen atom Atoms such as chlorine, bromine and fluorine.
  • Alkoxyl group An ethoxy group, a benzoyloxy group, a methoxyethylcarbamoylmethoxy group, a tetradecylcarbamoylmethoxy group, etc.
  • Aryloxy group A phenoxy group, a 4-methoxyphenoxy group, a 4-nitrophenoxy group, etc.
  • Acyloxy group An acetoxy group, a myristoyloxy group, a benzoyloxy group, etc.
  • Arylthio group a phenylthio group, a 2-butoxy-5-octylphenylthio group, a 2,5-dihexyloxyphenylthio group, etc.
  • Alkylthio group A methylthio group, an octylthio group, a hexadecylthio group, a benzylthio group, a 2-(diethylamino)ethylthio group, an ethoxycarbonylmethylthio group, an ethoxydiethylthio group, a phenoxyethylthio group, etc.
  • -N Z' A pyrazolyl group, an imidazolyl group, a triazolyl group, a tetrazolyl group, etc.
  • the coupler represented by Formula M-II may include, for example, the exemplary compounds No. 218 to No. 244 disclosed in Japanese Patent O.P.I. Publication No. 52138/1988. It may further include those disclosed in U.S. Patents No. 2,600,788, No. 3,061,432, No. 3,062,653, No. 3,127,269, No. 3,311,476, No. 3,152,896, No. 3,419,391, No. 3,519,429, No. 3,555,318, No. 3,684,514, No. 3,888,680, No. 3,907,571, No. 3,928,044, No. 3,930,861, No. 3,930,866 and No. 3,933,500, Japanese Patent O.P.I. Publications No.
  • the cyan coupler used in the present invention may include naphthol type, phenol type and imidazole type compounds.
  • the cyan coupler particularly preferably used in the present invention may include cyan couplers represented by the following Formulas C-I and C-II.
  • R c1 represents an alkyl group having 2 to 6 carbon atoms.
  • R c2 represent a ballast group.
  • Z c represents an atom or group capable of being split off upon reaction with an oxidized product of a color developing agent.
  • the alkyl group represented by R c1 may be straight-chain or branched, and may include those having a substituent.
  • the ballast group represented by R c2 is an organic group having the size and shape that impart to coupler molecules a bulkiness large enough for the coupler to be substantially undiffusible from the layer to which the coupler is applied, to other layer.
  • ballast group is a group represented by the following formula:
  • R c3 represents an alkyl group having 1 to 12 carbon atoms
  • Ar c represents an aryl group such as a phenyl group. This aryl group includes those having a substituent.
  • the cyan coupler represented by Formula C-I can be exemplified by the exemplary compounds PC-1 to PC-19 disclosed in Japanese Patent O.P.I. Publication No. 156748/1989, page 30, right upper column to page 31, left upper column, the exemplary compounds C-1 to C-28 disclosed in Japanese Patent O.P.I. Publication No. 249151/1987, and also the cyan couplers as disclosed in Japanese Patent Examined Publication No. 11572/1974, Japanese Patent O.P.I. Publications No. 3142/1986, No. 9652/1986, No. 9653/1986, No. 390465/1986, No. 50136/1986, No. 99141/1986 and No. 105545/1986. Examples are by no means limited to these.
  • R c1 represents an alkyl group or an aryl group.
  • R c2 represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group.
  • R c3 represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxyl group.
  • R c3 and R c1 may also combine to form a ring.
  • Z c represents a hydrogen atom or a group capable of being split off upon reaction with an oxidized product of a color developing agent.
  • the alkyl group represented by R c1 may preferably be an alkyl group having 1 to 32 carbon atoms, these of which may be straight-chain or branched, and may also include those having a substituent.
  • the aryl group represented by R c1 may preferably be a phenyl group, and may include those having a substituent.
  • the alkyl group represented by R c2 may preferably be an alkyl group having 1 to 32 carbon atoms. Such alkyl group may be straight-chain or branched, and may include those having a substituent.
  • the cycloalkyl group represented by R c2 may preferably be a cycloalkyl group having 3 to 12 carbon atoms. Such cycloalkyl group may include those having a substituent.
  • the aryl group represented by R c2 may preferably be a phenyl group, and may include those having a substituent.
  • the heterocyclic group represented by R c2 may preferably be a heterocyclic ring of 5 to 7 members, and may include those having a substituent. It may also be of a condensed form.
  • R c3 represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxyl group, where the alkyl group and the alkoxyl group may include those having a substituent.
  • R c3 may preferably be a hydrogen atom.
  • the ring formed by the combination of R c1 and R c3 may preferably include rings of 5 or 6 members, which can be exemplified by the following:
  • the group represented by Z c capable of being split off upon reaction with an oxidized product of a color developing agent may include a halogen atom, an alkoxyl group, an aryloxy group, an acyloxy group, a sulfonyloxy group, an acylamino group, a sulfonylamino group, an alkoxycarbonyoxy group, an aryloxycarbonyloxy group and an imide group, all of which may include those having a substituent. It may preferably be a halogen atom, an aryloxy group or an alkoxyl group.
  • cyan couplers described above a particularly preferred one is a cyan coupler represented by the following Formula C-II-A.
  • R A1 represents a phenyl group substituted with at least one halogen atom. Such a phenyl group may include a phenyl group further having a substituent other than the halogen atom.
  • R A2 has the same definition for R c1 in Formula C-II previously described.
  • X A represents a halogen atom, an aryloxy group or an alkoxyl group, and may include those having a substituent.
  • Typical examples of the cyan coupler represented by Formula C-II are the exemplary compounds C-1 to C-25 disclosed in Japanese Patent O.P.I. Publication No. 96656/1985, the exemplary compounds PC-II-1 to PC-II-31 disclosed in Japanese Patent O.P.I. Publication No. 156748/1989, pages 32, left lower column to page 34, left upper column, and besides the 2,5-diacylamino cyan couplers as disclosed in Japanese Patent O.P.I. Publication No. 178962/1987, page 7, right lower column to page 9, left lower column, Japanese Patent O.P.I. Publication No. 225155/1985, page 7, left lower column to page 10, right lower column, Japanese Patent O.P.I. Publication No.
  • Hydrophobic compounds such as the dye forming couplers as described above may usually be dissolved in a high-boiling organic solvent having a boiling point of about 150°C or above or a water-insoluble polymeric compound, optionally together with a low-boiling and/or water-soluble organic solvent to effect emulsification dispersion in a hydrophilic binder such as an aqueous gelatin solution using a surface active agent by the use of a dispersion means such as a homogenizer, a colloid mill, a flow-jet mixer and an ultrasonic apparatus, and thereafter the resulting emulsion may be added to the intended hydrophilic colloid layer.
  • the step of removing the low-boiling organic solvent at the same time of carrying out the dispersion may also be inserted.
  • a solvent with a dielectric constant of less than 6.0 may preferably be used as the high-boiling organic solvent.
  • any compounds can be used as the high-boiling organic solvent preferably used in the present invention so long as they are compounds with a dielectric constant of less than 6.0. No particular limitation may be required for its lower limit. In a preferred embodiment, the compounds may have a dielectric constant of 1.9 or more. They can be exemplified by esters such as phthalate and phosphate, organic acid amides, ketones and hydrocarbon compounds having dielectric constant of less than 6.0.
  • a high-boiling organic solvent having a vapor pressure of preferably not more than 0.5 mmHg at 100°C. It is more preferred to use phthalates or phosphates among such high-boiling organic solvents.
  • the organic solvent may be comprised of a mixture of two or more kinds. In this instance, the mixture may have the dielectric constant of less than 6.0.
  • the dielectric constant herein referred to indicates a dielectric constant measured at 30°C.
  • the phthalate advantageously used in the present invention may include a compound represented by the following Formula HA.
  • R H1 and R H2 each represent an alkyl group, an alkenyl group or an aryl group, provided that the total sum of the carbon atom number of the groups represented by R H1 and R H2 is from 9 to 32. More preferably, the total sum of the carbon atom number is from 16 to 24.
  • the alkyl group represented by R H1 and R H2 in the above Formula HA may be straight-chain or branched.
  • the aryl group represented by R H1 and R H2 may include a phenyl group, a naphthyl group, etc., and the alkenyl group, a hexenyl group, a heptenyl group, an octadecenyl group, etc. These alkyl group, alkenyl group and aryl group may each have a substituent or substituents.
  • the phosphate advantageously used in the present invention may include a compound represented by the following Formula HB.
  • R H3 , R H4 and R H5 each represent an alkyl group, an alkenyl group or an aryl group, provided that the total sum of the carbon atom number of the groups represented by R H3 , R H4 and R H5 is from 24 to 54.
  • R H3 , R H4 and R H5 are each an alkyl group, which may include a nonyl group, a n-decyl group, a sec-decyl group, a sec-dodecyl group and a t-octyl group.
  • the above high-boiling organic solvent can be exemplified by the exemplary organic solvents 1 to 22 disclosed in Japanese Patent O.P.I. Publication No. 166331/1987, page 41.
  • the polymer used for dispersing the couplers which is insoluble in water and soluble in an organic solvent, may include the following:
  • the number average molecular weight of these polymers may preferably be not more than 200,000, and more preferably from 5,000 to 100,000.
  • the proportion of the polymer to the hydrophobic compounds such as couplers may preferably be 1:20 to 20:1, and more preferably 1:10 to 10:1.
  • Examples of the polymer preferably used are shown below. Copolymers are shown together with their weight ratios.
  • gelatin As the binder (or protective colloid) used in the light-sensitive silver halide photographic material of the present invention, it is advantageous to use gelatin. Besides gelatin, it is also possible to use hydrophilic colloids such as gelatin derivatives, graft polymers of gelatin with other macromolecules, proteins, sugar derivatives, cellulose derivatives, and homopolymer or copolymer synthetic hydrophilic polymeric substances.
  • additives such as hardening agents, color contamination preventives, image stabilizers, ultraviolet absorbents, plasticizers, latexers, surface active agents, matting agents, lubricants and antistatic agents.
  • the gelatin coated on a support of the light-sensitive material of the present invention may preferably be in an amount of less than 7 g/m 2 in total. No particular limitation is required for its lower limit. In general, it may preferably be not less than 3 g/m 2 in view of physical properties or photographic performance.
  • the amount of gelatin can be determined in terms of the weight of gelatin containing 11.0 % of water, according to the method of measuring water content as described in the PAGI method.
  • the gelatin contained in the light-sensitive material of the present invention is hardened using a hardening agent.
  • a hardening agent there are no particular limitations on the hardening agent that can be used. It may include hardening agents known in the photographic industrial field, as exemplified by aldehyde type hardening agents, active vinyl type hardening agents, active halogen type hardening agents, epoxy type hardening agents, ethyleneimine type hardening agents, methane sulfonate type hardening agents, carbodiimide type hardening agents, isooxazole type hardening agents, and polymeric hardening agents.
  • the present invention can be particularly effective when the light-sensitive material of the present invention is used in direct-view light-sensitive materials such as color photographic papers or color copying light-sensitive materials on which there are severe demands for image storage stability.
  • images can be formed by carrying out color development processing known in the present industrial field.
  • the color developing agent used in the color developing solution may include aminophenol derivatives and p-phenylenediamine derivatives widely used in various color photographic processes.
  • known developing solution component compounds can be added in addition to the primary aromatic amine color developing agent previously mentioned.
  • the color developing solution may have a pH value of not less than 9, and preferably from about 10 to about 13.
  • Color developing may be carried out at a temperature of usually not lower than 15°C, and generally in the range of from 20°C to 50°C.
  • the color developing may preferably be carried out at 30°C or above.
  • Development processing may generally be carried out in 10 seconds to 4 minutes.
  • the processing may preferably be carried out in the range of from 10 seconds to 1 minute.
  • the processing may preferably be carried out in the range of from 10 seconds to 30 seconds.
  • the color developing solution may preferably be replenished in an amount of from 20 ml to 150 ml, more preferably from 20 ml to 120 ml, and still more preferably from 20 ml to 100 ml, per 1 m 2 of the light-sensitive material.
  • the present invention can be more effective when such low-replenishment running processing is carried out.
  • the light-sensitive material of the present invention is subjected to bleach-fixing.
  • the light-sensitive material is usually subjected to washing or stabilizing, or both of them in combination.
  • Em-1 10 90 0.67 Sodium thiosulfate SD-1 Em-2 30 70 0.46 " SD-2 Em-3 30 70 0.43 " SD-3 Em-4 99.5 0.5 0.67 Sodium thiosulfate + Sodium chloroaurate SD-1 Em-5 99.5 0.5 0.46 " SD-2 Em-6 99.5 0.5 0.43 " SD-3
  • the respective silver halide emulsions were chemically sensitized. After completion of the sensitization, STB-1 was added as an emulsion stabilizer in an amount of 2 x 10 -4 mol per mol of silver halide.
  • a laminated support comprising a paper support one side of which was coated with polyethylene and the first layer side on the other side of which was coated with polyethylene containing titanium oxide, layers with the constitution as shown below were formed by coating to give a multilayer light-sensitive silver halide color photographic material. Coating solutions were prepared in the following way.
  • a yellow coupler (Y-1), 0.67 g of an anti-stain agent (HQ-1) and 13.3 g of a high-boiling organic solvent (DNP), 60 ml of ethyl acetate was added to effect dissolution.
  • the resulting solution was emulsifyingly dispersed in 200 ml of an aqueous 10 % gelatin solution containing 10 ml of 10 % sodium alkylnaphthalenesulfonate, using a homogenizer to produce a yellow coupler dispersion.
  • the dispersion thus obtained was mixed together with a blue-sensitive silver chlorobromide emulsion (Em-1, 10 g in terms of silver) and a coating gelatin solution to give a first-layer coating solution.
  • a blue-sensitive silver chlorobromide emulsion Em-1, 10 g in terms of silver
  • Second-layer to seventh-layer coating solutions were also prepared in the same manner as the first-layer coating solution.
  • a compound (H-1) was added to the second and fourth layers, and (H-2) to the seventh layer.
  • surface active agents (SU-2), (SU-3) were added to make adjustment of surface tension.
  • the amounts of silver halide emulsions added are expressed in terms of silver.
  • the dye image stabilizers (1) and (2) were changed as shown in Table 1 to produce samples 102 to 140.
  • the above samples having been processed were stored for 2 weeks under sunlight (on an exposure stand) to examine fastness to light of dye images.
  • the fastness to light of dye images was evaluated on the following items.
  • Dye image stabilizer (1) Kq (M -1 s -1 ) Dye image stabilizer (2) Ks (M -1 s -1 ) Retention (2 w.) (%) Discoloration 116(X) Cp.QH-2 8x10 7 Cp .
  • Dye image stabilizer (1) Kq (M -1 s -1 ) Dye image stabilizer (2) Ks (M -1 s -1 ) Retention (2 w.) (%) Discoloration 133(Y) Ex.Q-34 7x10 8 Ex.R-47 3x10 -1 92 0.06 134(Y) Ex.Q-34 7x10 8 Ex.R-29 8 89 0.07 135(Y) Ex.Q-34 7x10 8 Ex.R-1 3x10 91 0.05 136(Y) Ex.Q-34 7x10 8 Ex.R-23 1x10 2 92 0.06 X: Comparative Example, Y: Present Invention
  • Improvements are also found to have been particularly remarkably achieved in both the dye retention and the prevention of discoloration in the light fastness tests when the compound having the radical-scavenging rate constant Ks of 10 -1 to 10 3 M -1 s -1 and the compound having the kq of not less than 10 8 M -1 s -1 are used at the same time.
  • Multilayer light-sensitive silver halide color photographic materials were produced in the same manner as in Example 1 except that the blue-sensitive silver chlorobromide emulsion Em-1 in the first layer, the green-sensitive silver chlorobromide emulsion Em-2 in the third layer and the red-sensitive silver chlorobromide emulsion Em-3 in the fifth layer were replaced with Em-4, Em-5 and Em-6, respectively.
  • Results obtained are shown in Table 2. Processing steps Temp. Time Color developing 35.0 ⁇ 0.3°C 45 sec. Bleach-fixing 35.0 ⁇ 0.5°C 45 sec. Stabilizing 30 to 34°C 90 sec. Drying 60 to 80°C 60 sec. Bleach-fixing solution Ferric ammonium ethylenediaminetetraacetate dihydrate 60 g Ethylenediaminetetraacetic acid 3 g Ammonium thiosulfate (aqueous 70 % solution) 100 ml Ammonium sulfite (aqueous 40 % solution) 27.5 ml Made up to 1 liter by adding water, and adjusted to pH 6.2 using potassium carbonate or glacial acetic acid.
  • Stabilizing solution 5-Chloro-2-methyl-4-isothiazolin-3-on 1.0 g Ethylene glycol 1.0 g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 g Ethylenediaminetetraacetic acid 1.0 g Ammonium hydroxide (aqueous 20 % solution) 3.0 g Ammonium sulfite 3.0 g Fluorescent brightening agent (4,4'-diaminostilbene disulfonic acid derivative) 1.5 g Made up to 1 liter by adding water, and adjusted using to pH 7.0 sulfuric acid or potassium hydroxide.
  • Dye image stabilizer (1) Kq (M -1 s -1 ) Dye image stabilizer (2) Ks (M -1 s -1 ) Retention (2 w.) (%) Discoloration 216(X) Cp.QH-2 8x10 7 Cp.RH-1 0 80 0.18 217(X) Cp.QH-2 8x10 7 Ex.R-47 3x10 -1 88 0.07 219(X) Cp.QH-2 8x10 7 Ex.R-1 3x10 87 0.08 220(X) Cp.QH-2 8x10 7 Ex.R-23 1x10 2 88 0.08 221(X) Cp.QH-2 8x10 7 Ex.R-4 5x10 3 84 0.11 222(X) Ex.Q-48 1x10 8 - - 78 0.15 223(X) Ex.Q-48 1x10 8 Cp.RH-1 0 79 0.14 224(Y) Ex.Q-48 1x10 8 Ex.R-47 3x10
  • Dye image stabilizer (1) Kq (M -1 s -1 ) Dye image stabilizer (2) Ks (M -1 s -1 ) Retention (2 w.) (%) Discoloration 233(Y) Ex.Q-34 7x10 8 Ex.R-47 3x10 -1 92 0.06 234(Y) Ex.Q-34 7x10 8 Ex.R-29 8 90 0.08 235(Y) Ex.Q-34 7x10 8 Ex.R-1 3x10 91 0.06 236(Y) Ex.Q-34 7x10 8 Ex.R-23 1x10 2 92 0.07 X: Comparative Example, Y: Present Invention
  • Example 2 The dye image stabilizers (1) and (2) in Example 2 were replaced as shown in Table 3.
  • the light-sensitive materials obtained were subjected to wedge exposure in the same manner as in Example 1, and were processed according to the color development processing steps like those in Example 2. Thereafter, the light-sensitive materials thus processed were stored for a month under sunlight, and then the same evaluation as in Example 1 was made.
  • Dye image stabilizer (1) Kq (M -1 s -1 ) Dye image stabilizer (2) Ks (M -1 s -l ) Retention (1 m.) (%) Discoloration 316(Y) Ex.Q-34 7x10 8 Ex.R-47 3x10 -1 77 0.32 317(Y) Ex.Q-34 7x10 8 Ex.R-29 8 75 0.33 318(Y) Ex.Q-34 7x10 8 Ex.R-1 3x10 77 0.35 319(Y) Ex.Q-34 7x10 8 Ex.R-23 1x10 2 78 0.32 X: Comparative Example, Y: Present Invention
  • magenta coupler MM-1 and the dye image stabilizers (1) and (2) in Example 2 were replaced as shown in Table 4. The same evaluation as in Example 1 was made.
  • Dye image stabilizer (1) Kq (M -1 s -1 ) Dye image stabilizer (2) Ks (M -1 s -1 ) [1] [2] [%] [3] 431(X) Cp.QH-2 8x10 7 Ex.R-47 3x10 -1 MM-4 88 0.06 432(X) Cp.QH-2 8x10 7 Ex.R-23 1x10 2 MM-4 88 0.07 433(X) EX.Q-48 1x10 8 - - MM-4 80 0.14 434(X) EX.Q-48 1x10 8 Cp.RH-1 0 MM-4 80 0.13 435(Y) EX.Q-48 1x10 8 Ex.R-47 3x10 -1 MM-4 94 0.05 436(Y) EX.Q-48 1x10 8 Ex.R-23 1x10 2 MM-4 93 0.06 [1]: Magenta coupler, [2]: Retention (2 weeks) [3]: Discoloration
  • pyrazolotriazole couplers MM-1, MM-3 and MM-4 which have a superior color reproduction quality to conventionally used 5-pyrazolone couplers but have an inferior fastness to light, improvements have been achieved particularly in both the dye retention and the prevention of discoloration in the light fastness when the compound according to the present invention having the kq of not less than 10 8 M -1 s -1 and the compound having the radical-scavenging ability are used at the same time.
  • Example 3 Samples produced in Example 3 were subjected to wedge exposure in the same manner as in Example 1, and thereafter processed according to the following processing steps until a color developing solution was replenished with a color developing solution replenisher in the amount three times the tank capacity of the color developing solution. Processing steps Temp. Time Color developing 35.0 ⁇ 0.3°C 45 sec. Bleach-fixing 35.0 ⁇ 0.3°C 45 sec. Stabilizing 30 to 34°C 90 sec. Drying 60 to 80°C 60 sec.
  • the color developing solution was replenished in an amount of 160 ml in the case of A, 110 ml in the case of B or 80 ml in the case of C, per 1 m 2 of the light-sensitive silver halide photographic material.
  • the above samples having been processed were stored for 2 weeks under sunlight (on an exposure stand) to examine the fastness to light of dye images.
  • the fastness to light of dye images was evaluated on the following items.
  • Dye image stabilizer (1) Kq (M -1 s -1 ) Dye image stabilizer (2) Ks (M -1 s -1) [1] [2] (%) [3] 516(X) Cp.QH-2 8x10 7 - - B 73 0.11 517(X) Cp.QH-2 8x10 7 Cp.RH-1 0 B 76 0.10 518(X) Cp.QH-2 8x10 7 Ex.R-47 3x10 -1 B 84 0.07 519(X) Cp.QH-2 8x10 7 Ex.R-29 8 B 83 0.09 520(X) Cp.QH-2 8x10 7 Ex.R-23 1x10 2 B 84 0.07 521(X) Ex.Q-48 1x10 8 - - B 73 0.10 522(X) Ex.Q-48 1x10 8 Cp.RH-1 0 B 75 0.09 523(Y) Ex.Q-48 1x10 8 Ex.R-47 3x10
  • Example 3 The amounts of gelatin as used in the first to seventh layers in Example 3 were changed as shown below, and also the dye image stabilizers (1) and (2) were replaced as shown in Table 6. Processing was carried out in the same manner as in Example 2, and evaluation was also made in the same manner as in Example 1. Amount of gelatin (g/m 2 ) Samples 601 to 609 Samples 610 to 618 Seventh layer 1.00 0.80 Sixth layer 0.40 0.35 Fifth layer 1.30 1.10 Fourth layer 0.94 0.90 Third layer 1.40 1.20 Second layer 1.20 1.00 First layer 1.20 1.00 Total 7.44 6.35
  • the present invention has made it possible to provide a light-sensitive silver halide photographic material improved in the fastness to light, of dye images and the prevention of stain on account of the feature that the compound having a singlet oxygen quenching rate constant kq of not less than 10 8 M -1 s -1 is contained and also the compound having a radical-scavenging ability is contained.

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Claims (6)

  1. Lichtempfindliches photographisches Silberhalogenid-Aufzeichnungsmaterial mit einem Schichtträger und einer darauf befindlichen, einen Farbstoff bildenden Kuppler enthaltenden Silberhalogenidemulsionsschicht, dadurch gekennzeichnet, daß die Silberhalogenidemulsionsschicht eine Verbindung mit Singulettsauerstoffquenchfähigkeit mit einer Quenchgeschwindigkeitskonstante Kq von nicht weniger als 1 x 108 M-1s-1 der Formel II-a-2:
    Figure 01300001
    worin bedeuten:
    Y' eine Gruppe von zur Vervollständigung eines 5- bis 8-gliedrigen heterocyclischen Rings erforderlichen nichtmetallischen Atomen;
    R10 eine Alkylgruppe, eine Cycloalkylgruppe, eine Alkenylgruppe, eine Arylgruppe, eine heterocyclische Gruppe, eine Acylgruppe, eine Brückenkohlenwasserstoffgruppe, eine Alkylsulfonylgruppe oder eine Arylsulfonylgruppe;
    R11 und R13 jeweils eine Elektronendonorgruppe einer Hammet-Konstante p von nicht mehr als 0, und
    R12 und R14 jeweils Wasserstoffatome;
    und eine Verbindung der Formel R
    Figure 01310001
    worin R15 für einen Substituenten steht und 1 eine ganze Zahl im Bereich von 0 bis 5 darstellt,
    aufweist,
    wobei der Wert Kq wie folgt bestimmt wird:
    Aus 3-(1,4-Epidioxyl-4-methyl-1,4-dihydro-1-naphthyl)-propionsäure in Ethanol als Lösungsmittel wird bei 35°C Singulettsauerstoff produziert;
    2,5-Diphenyl-3,4-benzofuran (DPBF) wird als Standardquenchsubstanz mit der zu messenden Substanz bereitgestellt;
    anschließend werden beide Substanzen einer konkurrierenden Reaktion mit dem Singulettsauerstoff unterworfen, wobei zur Bestimmung des Kq-Werts die zeitlichen Änderungen der Lichtabsorption bei der Absorptionswellenlänge des DPBF (λmax: 411 nm) verfolgt werden.
  2. Lichtempfindliches photographisches Silberhalogenid-Aufzeichnungsmaterial nach Anspruch 1, dadurch gekennzeichnet, daß die Verbindung der Formel R eine Radikaleinfanggeschwindigkeitskonstante ks von 1 x 10-1 bis 2 x 10-4 M-1s-1 aufweist.
  3. Lichtempfindliches photographisches Silberhalogenid-Aufzeichnungsmaterial nach Anspruch 1, dadurch gekennzeichnet, daß die Verbindung der Formel R aus einer solchen der Formel R-a oder R-b besteht:
    Figure 01320001
    worin R15 und R15' jeweils dieselbe Bedeutung wie R15 in Formel R aufweisen, A eine zweiwertige verbindende Gruppe darstellt, und a und a' jeweils für eine ganze Zahl von 0 bis 4 stehen, wobei gilt, daß im Falle, daß a oder a' = 2 oder mehr, mehrere Reste R15 und R15' gleich oder (voneinander) verschieden sein können, und wobei R15 und R15' unter Ringbildung miteinander kombiniert sein können;
    Figure 01320002
    worin R15' und R15" jeweils dieselbe Bedeutung besitzen wie R15 in Formel R, b und b' jeweils eine ganze Zahl von 0 bis 3 bedeuten, wobei gilt, daß im Falle, daß b oder b' = 2 oder mehr, mehrere Reste R15' oder R15" gleich oder (voneinander) verschieden sein können, und wobei sie zu einem Ring vereinigt sein können, und B und B' jeweils für eine Gruppe von nichtmetallischen Atomen stehen, die zusammen mit den Kohlenstoffatomen und C=C zur Vervollständigung eines 5- bis 7-gliedrigen heterocyclischen Rings erforderlich sind.
  4. Photographisches Aufzeichnungsmaterial nach Anspruch 1, wobei der Farbstoff bildende Kuppler der folgenden For-
    Figure 01330001
    worin bedeuten:
    Z eine Gruppe von zur Vervollständigung eines stickstoffhaltigen heterocyclischen Rings erforderlichen nichtmetallischen Atomen;
    X ein Wasserstoffatom oder eine bei der Reaktion mit einem Oxidationsprodukt einer Farbentwicklerverbindung abspaltbare Gruppe, und
    R ein Wasserstoffatom oder einen Substituenten.
  5. Photographisches Aufzeichnungsmaterial nach Anspruch 4, wobei der Farbstoff bildende Kuppler den folgenden Formeln M-II bis M-VII entspricht:
    Figure 01330002
    Figure 01340001
    Figure 01340002
    Figure 01340003
    Figure 01340004
    Figure 01340005
    oder
    Figure 01340006
    worin R1 bis R8 und X die bei Formel M-I für R bzw. X angegebenen Bedeutungen besitzen.
  6. Photographisches Aufzeichnungsmaterial nach Anspruch 1, wobei die Silberhalogenidemulsionsschicht Silberhalogenidkörnchen eines Silberchloridgehalts von nicht weniger als 90 Mol-% enthält.
EP91310285A 1990-11-10 1991-11-06 Photographisches lichtempfindliches Silberhalogenidmaterial Expired - Lifetime EP0486216B1 (de)

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DE4320445A1 (de) * 1993-06-21 1994-12-22 Agfa Gevaert Ag Farbfotografisches Aufzeichnungsmaterial
US5491054A (en) * 1994-12-22 1996-02-13 Eastman Kodak Company Photographic elements containing 2-equivalent pyrazolone magenta dye forming couplers and stabilizing compounds
US5484696A (en) * 1994-12-22 1996-01-16 Eastman Kodak Company Photographic elements containing 2-equivalent pyrazolone magenta dye forming couplers and fade reducing compounds
DE19750086A1 (de) * 1997-11-12 1999-05-20 Agfa Gevaert Ag Farbfotografisches Material
US6013429A (en) * 1998-02-27 2000-01-11 Eastman Kodak Company Photographic element with new singlet oxygen quenchers

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EP0457543A1 (de) * 1990-05-17 1991-11-21 Konica Corporation Photographisches lichtempfindliches Silberhalogenidmaterial geeignet zum Produzieren eines Farbbildes mit verbesserter Festigkeit

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DE3775428D1 (de) * 1986-02-06 1992-02-06 Konishiroku Photo Ind Lichtempfindliches photographisches silberhalogenidmaterial.
JPH02217845A (ja) * 1989-02-20 1990-08-30 Fuji Photo Film Co Ltd ハロゲン化銀カラー写真感光材料

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