EP0384670A2 - Méthode pour le traitement d'un matériau photosensible à halogénure d'argent pour photographie en couleurs - Google Patents

Méthode pour le traitement d'un matériau photosensible à halogénure d'argent pour photographie en couleurs Download PDF

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Publication number
EP0384670A2
EP0384670A2 EP90301711A EP90301711A EP0384670A2 EP 0384670 A2 EP0384670 A2 EP 0384670A2 EP 90301711 A EP90301711 A EP 90301711A EP 90301711 A EP90301711 A EP 90301711A EP 0384670 A2 EP0384670 A2 EP 0384670A2
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Prior art keywords
silver halide
processing
group
light
photographic material
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EP90301711A
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German (de)
English (en)
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EP0384670A3 (fr
Inventor
Shuji Murakami
Yukio Ohya
Syoji Matsuzaka
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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
    • G03C7/3003—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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/305—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers
    • G03C7/30541—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers characterised by the released group

Definitions

  • This invention relates to a method for processing a light-sensitive color photographic material suitable for full color photographing, particularly to a method for processing a negative-type light-sensitive silver halide color photographic material of which at least one color sensitive layer is a single layer.
  • Having broad exposure latitude refers to the fact that the gradation is good over wide exposure dose range from the shadow portion with little exposure dose to the high-light portion with much exposure dose in the so-called characteristic curve in which the exposure dose is taken on the axis of abscissa and the color formed density on the axis of ordinate.
  • Color negative film as different from color reversal film or color paper, is a light-sensitive material for which gradation is demanded to be strictly controlled over wider range of exposure dose, and for that reason, color negative films for photography commercially available at the present time are made to have an overlaid constitution comprising a plurality of emulsion layers of higher sensitivity layer containing greater grain sizes and lower sensitivity layer containing smaller grain sizes for the respective color sensitive layers to the light of blue color, green color and red color. Further, the so-called DIR compound for forming consequently a developing inhibitor through the reaction with the oxidized product of the developing agent is employed.
  • Such technique is inherent in color negative film, and particularly the DIR compound improves not only gradation but also sharpness, graininess, color reproducibility, and is essential in color negative film.
  • a color negative film has an overlaid constitution by use of a plurality of emulsion layers containing silver halide grains with different grain sizes as described above, and further that it further strictly controls gradation by use of a DIR compound, stability to processing conditions is inferior (because a color negative film is processed under various laboratories as compared with color reversal film, developing processing is conducted under processing conditions with great width of fluctuation. Therefore, a color negative film is particularly demanded to have high degree of stability to fluctu ation in processing conditions.), etc., it has drawbacks such that gradation is deteriorated, color reproducibility and tone reproducibility are deteriorated, etc.
  • the present invention has been accomplished in view of the task of the prior art as mentioned above, and its object is to provide a method for processing a light-sensitive silver halide color photographic material which can obtain sufficient color formed density to give an image excellent in tone reproducibility, color reproducibility and also sharpness, even if developing processing is made more rapid.
  • the method for processing a light-sensitive silver halide color photographic material comprises processing a light-sensitive silver halide color photogra phic material, comprising a support and silver halide emulsion layers which are respectively blue-sensitive, green-sensitive or red-sensitive and are provided on the support, said material having a DIR compound, and at least one of said blue-, green- and red-sensitive silver halide emulsion layers having a single layer constitution, within a color developing time of 120 seconds.
  • the DIR compound to be used in the light-sensitive material of the present invention is a compound which eliminates a developing inhibitor or a compound capable of releasing a developing inhibitor through the reaction with the oxidized product of the color developing agent.
  • the above-mentioned compound capable of releasing a developing inhibitor may be one which releases the developing inhibitor either imagewise or non-imagewise.
  • Imagewise release may be effected by, for example, the reaction with the oxidized product of the developing agent, while non-imagewise release by utilizing, for example, the TIME group as described below.
  • Y may be typically represented by the formulae (D-2) to (D-20) set forth below.
  • Rd 1 represents hydrogen atom, a halogen atom or an alkyl, alkoxy, acylamino, alkoxycarbonyl, thiazolidinylideneamino, aryloxycarbonyl, acyloxy, carbamoyl, N-alkylcarbamoyl, N,N-dialkylcarbamoyl, nitro, amino, N-arylcarbamoyloxy, sulfamoyl, N-alkylcarbamoyloxy, hydroxy, alkoxycarbonylamino, alkylthio, arylthio, aryl, heterocyclic, cyano, alkylsulfonyl or aryloxycarbonylamino group.
  • n 0, 1 or 2
  • the respective Rd 1 's may be either the same or different.
  • the total carbon atoms contained in n Rdi's may be 0 to 10.
  • the total number of the carbon atoms contained in Rd 1 in the formula (D-6) may be 0 to 15.
  • X represents oxygen atom or sulfur atom.
  • Rd 2 represents an alkyl group, an aryl group or a heterocyclic group.
  • Rd 3 represents hydrogen atom, or an alkyl, cycloalkyl, aryl or heterocyclic group
  • Rd4 represents hydrogen atom, a halogen atom or an alkyl, cycloalkyl, aryl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkanesulfonamide, cyano, heterocyclic, alkylthio or amino group.
  • Rd 1 , Rd 2 , Rd 3 or Rd4 represents an alkyl group
  • the alkyl group may include those having substituents, and may be either straight or branched.
  • Rd 1 , Rd 2 , Rd 3 or Rd 4 represents an aryl group
  • the aryl group may include those having substituents.
  • the heterocyclic group may include those having substitu ents, preferably 5- or 6-membered monocyclic or fused rings containing at least one selected from nitrogen atom, oxygen atom and sulfur atom as the hetero atom, that may be selected from the groups of, for example, pyridyl, quinolyl, furyl, benzothiazolyl, oxazolyl, imidazolyl, thiazolyl, triazolyl, benzotriazolyl, imide, oxazine.
  • the carbon atoms contained in Rd 2 in the formula (D-8) may be 0 to 15.
  • the total carbon atoms contained in Rd 3 and Rd 4 may be 0 to 15.
  • the TIME group is a group, bound to the coupling position of A and being cleavable through the reaction with the oxidized product of the color developing agent, which is a group cleaved successively after cleavage from the coupler and until finally can release the INHIBIT groups with adequate control; n is 1 to 3, and when it is 2 or 3, the respective TIME groups may be either the same or different.
  • the INHIBIT group is a group which becomes a developing inhibitor by the above-mentioned release (e.g. the group represented by the above formulae (D-2) to (D-9)).
  • the -TIME group may be typically represented by the formulae (D-11) to (D-19) set forth below.
  • Rd 5 represents hydrogen atom, a halogen atom or an alkyl, cycloalkyl, alkenyl, aralkyl, alkoxy, alkoxycarbonyl, anilino, acylamino, ureido, cyano, nitro, sulfonamide, sulfamoyl, carbamoyl, aryl, carboxy, sulfo, hydroxy or alkanesulfonyl group.
  • Rds's may be mutually bonded together to form a fused ring.
  • Rd 6 represents an alkyl, alkenyl, aralkyl, cycloalkyl, heterocyclic or aryl group.
  • Rd 7 represents a hydrogen atom or an alkyl, alkenyl, aralkyl, cycloalkyl, heterocyclic or aryl group.
  • Each of Rd s and Rd 9 in the formulae (D-19) represents hydrogen atom or an alkyl group (preferably an alkyl group having 1 to 4 carbon atoms), k in the formulae (D-11) and (D-15) to (D-18) represents an integer of 0, 1 or 2, 1 in the formulae (D-11) to (D-13). (D-15) and (D-18) represents an integer of 1 to 4, m in the formula (D-16) represents an integer of 1 or 2. When I and m are 2 or more, the respective Rds and Rd 7 may be either the same or different. n in the formula (D-19) represents an integer of 2 to 4, and Rd 8 and Rd s in number of n may be each the same or different.
  • B in the formulae (D-16) to (D-18) represents oxygen atom or (Rd 6 represents the same meaning as already defined), and in the formula (D-16) may be either a single bond or a double bond, and m is 2 in the case of the single bond and m is 1 in the case of the double bond.
  • T represents a component which cleaves SR( ⁇ T 2 ) ⁇ m -INHIBIT
  • SR a component which forms ( ⁇ T 2 ) ⁇ m INHIBIT through the reaction with the oxidized product of the developing agent after formation of SR( ⁇ T 2 ) ⁇ m INHIBIT
  • T 2 a component which cleaves INHIBIT after formation of ( ⁇ T 2 ) ⁇ m INHIBIT
  • INHIBIT a developing inhibitor and I and m each 0 or 1.
  • the component represented by SR may be one which can form the component as mentioned above through the reaction with the oxidized product of the developing agent, and may include, for example, a coupler component which undergoes the coupling reaction with the oxidized product of the developing agent or a redox component which undergoes the redox reaction with the oxidized product of the developing agent.
  • coupler component there may be included yellow couplers, magenta couplers, cyan couplers such as acylacetanilides, 5-pyrazolones, pyrazoloazoles, phenols, naphthols, acetophenones, indanones, carbamoylacetanilides, 2(5H)-imidazolones, 5-isoxazolones, uracils, homophthalimides, oxazolones, 2,5-thiadiazoline-1,1-dioxides, triazolothiadiazines, indoles, etc., and otherwise those which form various dyes or form no dye.
  • yellow couplers such as acylacetanilides, 5-pyrazolones, pyrazoloazoles, phenols, naphthols, acetophenones, indanones, carbamoylacetanilides, 2(5H)-imidazolones, 5-isoxazolones,
  • the ( ⁇ T 1 ) ⁇ -SR( ⁇ T 2 ) ⁇ m INHIBIT should be preferably bonded to the active site of the component A of the formula (D-1).
  • SR When SR is a coupler component, SR is bonded to ( ⁇ T 1 ( and ( ⁇ T 2 ) ⁇ m INHIBIT so as to function for the first time as the coupler after cleavage from ( ⁇ T 1 ) ⁇ .
  • the coupler component is a phenol or a naphthol and the oxygen atom of hydroxyl group is a 5-pyrazolone
  • the oxygen atom at the 5-position, or the nitrogen atom at the 2-position of the enantiomer, and also the oxygen atom of hydroxyl group of the enantiomer in acetophenones or indanones should be preferably bonded to SR ( ⁇ T 1 ) ⁇ , and ( ⁇ T 2 ) ⁇ m INHIBIT to the active site of the coupler.
  • SR is a redox component
  • its examples may include hydroquinones, catechols, pyrogallols, aminophenols (e.g. p-aminophenols, o-aminophenols), naphthalenediols (e.g. 1,2-naphthalenediols, 1,4-naphthalenediols, 2,6-naphthalenediols), or aminonaphthols (e.g. 1,2-aminonaphthols, 1,4-aminonaphthols, 2,6-aminonaphthols), etc.
  • aminophenols e.g. p-aminophenols, o-aminophenols
  • naphthalenediols e.g. 1,2-naphthalenediols, 1,4-naphthalenediols, 2,6-naphthalenediols
  • aminonaphthols e.g. 1,2-
  • SR is a redox component
  • SR is bonded to (T ) ⁇ and ( ⁇ T 2 ) ⁇ m INHIBIT so as to function for the first time as the redox component after cleavage from (T2 ) ⁇ .
  • Examples of the group represented by T, and T 2 may include those represented by the formulae (D-11) to (D-19) as described above.
  • DIR compounds preferable are those wherein Y is represented by the formula (D-2), (D-3), (D-8), (D-10) or (D-20), and among (D-10) and (D-20), those wherein INHIBIT is represented by the formula (D-2), (D-3), (D-6) (particularly when X of (D-6) is oxygen atom), or (D-8) are preferred.
  • coupler residue represented by A in the formula (D-1) yellow color image forming coupler residues, magenta color image forming coupler residues, cyan color image forming coupler residues and no color exhibiting coupler residues may be included.
  • DIR compounds to be used in the present invention the compounds as shown below may be included, but these are not limitative of the invention.
  • DIR compounds which can be used in the present invention, including these are described in U.S. Patents 4,234,678, 3,227,554, 3,617,291, 3,958,993, 4,149,886, 3,933,500, Japanese Unexamined Patent Publications Nos. 56837/1982 and 13239/1976, U.S. Patents 2,072,363 and 2,070,266, Research Disclosure No. 21228, December, 1981, etc.
  • the DIR compound should be preferably used in an amount of 0.0001 to 0.1 mole, particularly 0.001 to 0.05 mole, per mole of silver halide.
  • the place in which the DIR compound to be used in the present invention is added may be any place which can affect developing of the silver halide in the emulsion layer of single layer constitution, preferably in a silver halide emulsion layer, more preferably in an emulsion layer having a single layer constitution.
  • the constitution that the color sensitive layer is a single layer is also inclusive of the case when a plurality of emulsion layers which are the same in color sensitivity, being the same in the kind of the couplers contained in the emulsion layers, grain sizes of the silver halide grains, the halogen compositions and crystal habits, and also the ratio of the coupler to the silver halide, are arranged as continuous layers.
  • the same in color sensitivity or “the same color sensitivity” may be the same in the point of, for example, blue sensitivity, green sensitivity, red sensitivity, and is not required to be totally the same in spectral sensitivity characteristics.
  • the blue-sensitive layer should be preferably a single layer, and further preferably, both the blue-sensitive layer and the green-sensitive layer should be single layers. Particularly, all of the blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layers should be preferably single layers, respectively.
  • the same color sensitive layer has a single layer constitution
  • the number of the layers coated of the light-sensitive layer can be reduced as compared with the overlaid constitution of the prior art, whereby the film can be made thinner. Therefore, production efficiency, sharpness are improved, and graininess is also improved.
  • the film thickness should be preferably 20 to 3 um, particularly 15 to 5 ⁇ m, after drying.
  • the exposure latitude is the width of light received at which the exposure effect with a significant difference can be exhibited, particularly the exposure region from the highlight to the deep shadow in the characteristic curve, and is determined by the method defined in "Shashin no Kagaku” (Chemistry of Photography), p. 393 (Shashin Kogyo Shuppansha, 1982).
  • the light-sensitive material should be preferably one having an exposure latitude measured according to the method as described above of 3.0 or more, particularly 3.0 to 8.0.
  • the means for making the exposure latitude of the silver halide emulsion layer which is a single layer wide, e.g. 3.0 or more, it is possible to use the method in which silver halide grains with different sensitivities are used as a mixture. Specifically, there may be included, for example, the method in which silver halide grains. with different grain sizes are used as a mixture, and the method in which the desensitizer is contained in at least a part of the silver halide grains.
  • the grain group having a larger mean grain size should preferably be in the range of 0.2 to 2.0 ⁇ m and the grain group having a smaller mean grain size, 0.05 to 1.0 um, and the mean grain size of the latter group is smaller than that of the former group.
  • one or more of silver halide grains having an intermediate mean grain size may be combined.
  • the mean grain size of the silver halide grains with the maximum mean grain size should be preferably 1.5 to 40 times as that of the silver halide grain with the minimum mean grain size.
  • silver halide grains with different mean grain sizes can be also used as a mixture, but by using silver halide grains containing a desensitizer in place of the low sensitivity silver halide grains with small grain sizes, the mean grain size difference can be made smaller without changing the sensitivity of the silver halide grains, and further it becomes possible to use silver halide grains with equal mean grain size and different sensitivities.
  • the exposure latitude can be obtained even if the fluctuation coefficient of the grains as a whole may be made smaller.
  • these silver halide grains with small fluctuation coefficient exposed to the same environment are preferably stabilized in photographic performances relative to changes with lapse of time and fluctuations in developing processing. Further, in aspect of production technique, it becomes also possible to sensitize chemically a mixed system of silver halide grains with different sensitivities in the same batch.
  • desensitizer in addition to metal ions, various ones such as antifoggants, stabilizers, desensitizing dyes, etc. can be used.
  • the metal ion doping method is preferred.
  • the metal ion to be used for doping there may be included the metal ions of the groups Ib, Ilb, Illa, lllb, I ⁇ b, Va, VIII in the periodic table of elements.
  • Preferable metal ions may include Au, Zn, Cd, TI, Sc, Y, Bi, Fe, Ru, Os, Rh, Ir, Pd, Pr, Sm and Yb. Particularly, Rh, Ru, Os and Ir are preferred.
  • These metal ions can be used as, for example, halogeno complexes, etc., and the pH of the AgX system during doping should be preferably 5 or less.
  • the amount of these metal ions doped will differ variously depending on the kind of the metal ion, the grain size of the silver halide grains, the doping position of the metal ion, the desired sensitivity, etc., but may be preferably 10- 17 to 10- 2 mole, further 10- 12 to 10- 3 mole, particularly 10- 9 to 10- 4 mole, per mole of AgX.
  • the silver halide grains with different doping conditions are adjusted in conditions to be provided for practical application, these can be also made up in the same batch by mixing at a predetermined ratio and subjected to chemical sensitization.
  • the respective silver halide gains receive the sensitizing effects based on their qualities, whereby an emulsion having a broad exposure latitude depending on the sensitivity difference and the mixing ratio can be obtained.
  • azoles e.g. benzothiazolium salt, indazoles, triazoles, benztriazoles, benzimidazoles, etc.
  • heterocyclic mercapto compounds e.g. mercaptotetrazoles, mercaptothiazoles, mercaptothiadiazoles, mercaptobenzthiazoles, mercaptobenzimidazoles, mercaptopyrimidines, etc.
  • azaindenes e.g. tetraazaindenes, pentaazaindenes, etc.
  • decomposed products of nucleic acids e.g. adenine, guanine, etc.
  • benzenethiosulfonates thioketo compounds, and others.
  • cyanine dyes there may be included cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes, etc.
  • the position where the desensitizer exists it should be preferably mixed internally of the silver halide grains, and its distribution may be either uniform, localized at the central portion of grain or the intermediate positions, etc., or also gradually reduced from the central portion of grain toward outside in viewpoint of the storability of the light-sensitive material and the stability of the digestion stability of the coating liquid.
  • the desensitizer exists as localized at the central portion of grain is preferable, and by use of the system in which seed grains with small fluctuation coefficient are used, the steps of grain growth et seq can be proceeded in the same batch.
  • the light-sensitive material of the present invention should desirably have at least one color sensitive layer (e.g. blue-sensitive layer) containing AgX grains containing a desensitizer.
  • a color sensitive layer e.g. blue-sensitive layer
  • the blue-sensitive layer contains AgX grains containing a desensitizer, more preferably when the blue-sensitive layer and the green-sensitive layer contain them, most preferably when all of the color sensitive layers contain them.
  • the fluctuation coefficient defined by the ratio S/ r of the standard deviation of grain size (S) as the silver halide grains contained in the respective silver halide emulsion layers and the mean grain size ( r ) should be preferably 0.4 or less, more preferably 0.33 or less, further preferably 0.25 or less, particularly preferably 0.20 or less.
  • the mean grain size ( r ) is defined by the following formula when the number of grains with a grain size ri (in the case of a cubic silver halide grain, its length of one side, or in the case of a grain with other shape than cubic, the length of one side of the cube calculated to have the same volume) is ni:
  • grain size distribution can be determined according to the method described in the essay of Tribel and Smith in “Empirical Relationship between Sensitometry Distribution and Grain Size Distribution in Photography", The Photographic Journal, vol. LXXIX (1949), p.p. 330 - 338.
  • any of conventional silver halide emulsions can be used, but a silver halide containing substantially iodine in the halogen composition (e.g. silver iodobromide, silver iodochlorobromide) may be preferable, particularly preferably silver iodobromide with respect to sensitivity.
  • the amount of iodine may be preferably I mole % or more and 20 mole % or less, particularly 3.5 mole % or more 12 mole % or less.
  • a coreishell type silver halide emulsion to be used in the present invention preferably has a grain structure comprising two or more phases different in silver iodide content and comprises silver halide grains in which a phase containing a maximum silver iodide content (referred to as “core”) is other than the outermost surface layer (referred to as "shell").
  • core a phase containing a maximum silver iodide content
  • shell the outermost surface layer
  • the content of silver iodide in an inner phase (core) having the maximum silver iodide content is preferably 6 to 40 mole %, more preferably 8 to 40 mole %, particularly preferably 10 to 40 mole %.
  • the content of silver iodide in the outermost surface layer is preferably less than 6 mole %, more preferably 0 to 4.0 mole %.
  • a ratio of the shell portion in the core/shell type silver halide grains is preferably 10 to 80 %, more preferably 15 to 70 %, particularly preferably 20 to 60 % in terms of volume.
  • a ratio of the core portion is preferably, in terms of volume, 10 to 80 %, more preferably 20 to 50 % based on the whole grains.
  • Difference of silver iodide content between the core portion having higher silver iodide content and the shell portion having less silver iodide content of the silver halide grains may be clear with sharp boundary or may be hazy where boundary is not clear and the content continuously changes. Also, those having an intermediate phase with silver iodide content between those of the core portion and the shell portion, between the core and the shell, may be preferably used.
  • a volume of the intermediate phase is preferably 5 to 60 %, more preferably 20 to 55 % based on the whole grain.
  • Differences of the silver iodide content between the shell and the intermediate phase, and between the intermediate phase and the core are each preferably 3 mole % or more and the difference of the silver iodide content between the shell and the core is preferably 6 mole % or more.
  • the core/shell type silver halide emulsion can be prepared according to the known methods as disclosed in Japanese Provisional Patent Publications No. 177535/1984, No. 138538/1985. No. 52238/1984, No. 143331/1985, No. 35726/1985 and No. 258536/1985.
  • soluble silver salt and soluble halide are generally used, but as is clear from the examples mentioned below, iodide salts are preferably used in t!:e form of silver iodide fine crystals in viewpoint of preservability and processing stability of the light-sensitive material.
  • silver iodobromide fine crystals having high Agl content are similarly and preferably used as the silver iodide fine crystals.
  • Distribution condition of the silver iodide in the above core/shell type silver halide grains can be determined by various physical measuring method and, for example, it can be examined by the measurement of luminescence at low temperature or X-ray diffraction method as described in Lecture Summary of Annual Meeting, Japanese Photographic Association, 1981.
  • the core/shell type silver halide grain may be any shape of normal crystal such as cubic, tetradecahedral and octahedral, or twinned crystal, or mixtures thereof, but preferably normal crystal grains.
  • Said emulsion can be chemically sensitized in conventional manner, and optically sensitized to a desired wavelength region by use of a sensitizing dye.
  • silver halide emulsion antifoggants, stabilizers, etc. can be added.
  • gelatin can be advantageously used as the binder for said emulsion.
  • the emulsion layer and other hydrophilic colloid layers can be hardened, and also a plasticizer and a dispersion (latex) of a water-soluble or difficultly soluble synthetic polymer can be contained therein.
  • couplers are used.
  • colored couplers having the effect of color correction, competitive couplers and compounds releasing photographically useful fragments such as developer, silver halide solvent, toning agents, film hardeners, antifoggants, chemical sensitizers, spectral sensitizers and desensitizers through the coupling with the oxidized product of the developing agent.
  • auxiliary layers such as filter layer, antihalation layer, anti-irradiation layer, etc. can be provided.
  • a dye which flows out from the light-sensitive material or bleached during developing processing may be also contained.
  • formalin scavenger fluorescent brightener, matte agent, lubricant, image stabilizer, surfactant, color fog preventive, developing accelerator, developing retarder, bleaching accelerator, etc. can be added.
  • papers laminated with polyethylene, etc., polyethylene terephthalate film, baryta film, cellulose triacetate, etc. can be used.
  • the light-sensitive material of the present invention is particularly useful as the negative-type light-sensitive material.
  • the time required for said color developing processing is within 120 seconds, preferably within the range from 20 to 120 seconds, more preferably from 40 to 100 seconds.
  • aromatic primary amine type developing agent preferably aromatic primary amine type developing agent is used, and various known ones used widely in color photographic processes may be included.
  • These developers include aminophenol type and p-phenylene diamine type derivatives. These compounds are generally used in the forms of salts, such as hydrochlorides or sulfates, because they are more stable than free state.
  • aminophenol type developers may include o-aminophenol, p-aminophenol, 5-amino-2-oxy- toluene, 2-amino3-oxy-toluene, 2-oxy-3-amino-1,4-dimethyl-benzene, etc.
  • p-phenylenediamine type developers are N,N -dialkyl-p-phenylenediamine type compounds, and the alkyl group and the phenylene group may be also substituted.
  • particularly useful compounds can include N,N'-dimethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, N,N'-dimethyl-p-phenylenediamine hydrochloride, 2-amino-5-(N-ethyl-N-dodecylamino)-toluene, N-ethyl-N- ⁇ -methanesulfoneamidoethyl-3-methyl-4-aminoaniline sulfate, N-ethyl-N-p- hydroxyethylaminoaniline, 4-amino-3-methyl-N,N'-diethylaniline, 4-amino-N-(2-methoxye
  • aromatic primary amine color developers various compounds disclosed on pages 79 to 86 in Japanese Patent Application No. 162885/1986 can be used.
  • the above-mentioned aromatic primary amine color developing agent may be contained within the range preferably of 2 x 10- 2 or more, more preferably from 2.5 x 10- 2 to 2 x 10- 1 mole, particularly from 3 x 10- 2 to 1 x 10 -1 mole, per one liter of developing solution.
  • sodium sulfite sodium hydrogen sulfite, potassium sulfite, potassium hydrogen sulfite, etc.
  • sodium sulfite sodium hydrogen sulfite
  • potassium sulfite potassium hydrogen sulfite
  • etc. which may be preferably used within the range from 0.1 to 40 g/liter, more preferably from 0.5 to 10 g/liter.
  • Hydroxylamine may be used as pair salt in hydrochlorides, sulfates, etc., preferably within the range from 0.1 to 40 g/liter, more preferably from 0.5 to 10 g/liter.
  • the inhibitor there are halides such as sodium bromide, potassium bromide, sodium iodide, potassium iodide, etc., and as the organic inhibitor, there may be included the compounds shown below, and the amount added may be within the range from 0.005 to 20 giliter, preferably from 0.01 to g/liter.
  • an organic inhibitor those disclosed on pages 88 to 105 in Japanese Patent Application No. 162885/1986 can be used.
  • the color developing solution should preferably contain the compound of the following formula (IS).
  • Rs 1 represents -OH
  • -ORS 4 or Rs 4 and Rs s each represent an alkyl group
  • the alkyl group represented by each of Rs 4 and R S 5 include also those having substituents (e.g. hydroxyl group, aryl group such as phenyl group, etc.), and methyl, ethyl, propyl, butyl, benzyl, S-hydroxyethyl, dodecyl groups, etc. may be included.
  • Rs 2 and Rs 3 each represent -H or and Rs 6 represents an alkyl or aryl group, and the alkyl group represented by Rs 6 may include, for example, a long chain alkyl group such as undecyl group, etc.
  • the compound represented by the formula (IS) is typically a citrazinic acid derivative
  • Z represents -CH the compound represented by the formula (IS) is typically a benzoic acid deivative
  • the 6-membered ring as the whole compound may also include those having substituents such as halogen atoms, etc.
  • the compound represented by the formula (IS) should be preferably used in an amount of, for example, 0.1 g to 50 g, more preferably 0.2 g to 20 g, per one liter of the color developing solution.
  • color developing solution to be used in the present invention further various components conventionally added can be incorporated as desired, including, for example, alkali agents such as sodium hydoxide, sodium carbonate, etc., alkali metal thiocyanates, alkali metal halides, benzyl alcohol, water softeners and thickeners, and developing accelerators, etc.
  • alkali agents such as sodium hydoxide, sodium carbonate, etc.
  • alkali metal thiocyanates alkali metal halides
  • alkali metal halides alkali metal halides
  • benzyl alcohol benzyl alcohol
  • water softeners and thickeners water softeners and thickeners
  • developing accelerators etc.
  • anti-staining agents As other additives than those mentioned above to be added in the above-mentioned developing solution, there are anti-staining agents, anti-sludge agents, preservatives, overlaying effect accelerators, chelating agents, etc.
  • the color developing solution should preferably used as pH 9 or higher, particularly at pH 9 to 13.
  • the processing temperature in the color developing step should be preferably 10 to 65 °C, more preferably 25 to 45 C.
  • the processing of the light-sensitive photographic material of the present invention is not particularly limited, but various processing methods are applicable.
  • organic acids such as aminopolycarboxylic acid or oxalic acid, citric acid, etc. having metal ions such as iron, cobalt, copper, etc. coordinated have been generally known.
  • aminopolycarboxylic acid may include the following:
  • the bleaching solution and the bleach-fixer can be used at pH 0.2 to 9.5, preferably 4.0 or higher, more preferably 5.0 or higher.
  • the processing temperature may be used at 20 C to 80 C, desirably at 40 C or higher.
  • the bleaching solution can contain various additives together with the bleaching agent as mentioned above (preferably organic acid ferric complexes).
  • additives particularly alkali halides or ammonium halides, such as potassium bromide, sodium bromide, sodium chloride, ammonium bromide, potassium iodide, sodium iodide, ammonium iodide, etc. should be desirably contained.
  • pH buffering agents such as borates, oxalates, acetates, carbonates, phosphates, etc.
  • solubilizing agents such as triethanolamine, etc.
  • bleach-fixers comprising compositions having halogen compounds such as potassium bromide added in small amounts, or bleach-fixers comprising compositions having halogen compounds such as potassium bromide or ammonium bromide added contrariwise in large amounts, and further special bleach-fixers comprising combinations of bleaching agents and large amounts of halogen compounds such as potassium bromide, etc.
  • halogen compounds there can be also used, other than potassium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, ammoium bromide, potassium iodide, sodium iodide, ammonium iodide, etc.
  • silver halide fixer to be contained in the bleach-fixer
  • compounds which form water soluble complexes by the reaction with silver halides as used in conventional fixing processing are representative, for example, thiosulfates such as potassium thiosulfate, sodium thiosulfate, ammonium thiosulfate, thiocyanates such as potassium thiocyanate, sodium thiocyanate, ammonium thiocyanate, thiourea, thioether, and bromides and iodides of high concentrations, etc.
  • These fixers can be used in amounts within the range which can dissolve 5 g/liter or more, preferably 50 g/liter or more, more preferably 70 g/liter or more.
  • pH buffering agents comprising various kinds of salts such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide, etc. can be contained singly or in a combination of two or more kinds. Further, various fluorescent brighteners, defoaming agents, surfactants or antifungal agents can be contained.
  • preservatives such as hydroxylamine, hydrazine, sulfites, metabisulfites, bisulfuric acid adducts of aldehyde or ketone compounds, etc.; organic chelating agents such as acetylacetone, phosphonocarboxylic acid, polyphosphoric acid, organic phosphonic acid, oxycarboxylic acid, polycarboxylic acid, dicarboxylic acid and aminopolycarboxylic acid, etc.; or stabilizers such as nitroalcohol, nitrates, etc.; solubilizing agents such as alkanolamine, etc.; anti-staining agents such as organic amines, etc.; other additives; organic solvents such as methanol, dimethylformamide, dimethyl sulfoxide, etc.
  • bleaching or bleaching and fixing processing may be also performed after performing water washing or rinsing and stopping, etc. after color developing, and also a pre-bath containing a bleaching accelerator may be used as the processing liquor prior to bleaching or bleaching and fixing.
  • the processing temperatures in various processing steps other than developing, for example, bleaching and fixing (or bleaching and fixing), and further water washing or stabilizing substituting for water washing, etc. which are performed, if necessary, should be preferably 20° C to 80 C, more preferably 40 C or higher.
  • aqueous gelatin Into a reaction vessel in which an aqueous gelatin had been thrown, while controlling the pAg and the pH in the reaction vessel and also controlling the addition time, were added at the same time an aqueous silver nitrate solution, an aqueous potassium iodide solution and an aqueous potassium bromide solution, and then precipitation and desalting were practiced by use of a pH coagulatable gelatin, followed by addition of gelatin to prepare a seed emulsion.
  • the emulsion obtained is called NE-1.
  • a seed emulsion was prepared in the same manner as described above except for adding K 3 RhCI G in the reaction vessel (NE-2).
  • the emulsions and their contents are shown in Table 1.
  • the amounts coated are indicated in the amount represented in g/m 2 unit calculated on silver for silver halide and colloidal silver, the amount represented in gim 2 unit for the additive and gelatin, and further in moles per mole of silver within the same layer for sensitizing dye, coupler and DIR compound.
  • the emulsion contained in each color sensitive emulsion layer was applied with optimum sensitization with sodium thiosulfate and chloroauric acid.
  • surfactants were added as the coating aid.
  • Sample No. 102 was prepared in the same manner as Sample No. 101 except for omitting G-2 in Sample No. 101, changing the emulsion contained in G-1 to a mixture of equal moles of EM-1 and EM-2, increasing the amounts used of the emulsion, the gelatin and TCP contained in G-1 by 30 % (the amounts of the sensitizing dye, coupler and DIR compound of G-1 per mole of silver halide are the same as in Sample No. 01).
  • Sample No. 103 was prepared in the same manner as Sample No. 102 except for omitting B-2 in Sample No. 102, changing the emulsion contained in B-1 to a mixture of equal moles of EM-1 and EM-2, further increasing the amounts used of the emulsion, the gelatin and TCP contained in B-1 by 15 % (the amounts of the sensitizing dye and coupler of B-1 per mole of silver halide are the same as in Sample No. 102).
  • Sample No. 104 was prepared in the same manner as Sample No. 103 except for omitting R-2 in Sample No. 103, changing the emulsion contained in R-1 to a mixture of equal moles of EM-1 and EM-2, further increasing the amounts used of the emulsion, the gelatin and DOP contained in R-1 by 25 % (the amounts of the sensitizing dye, coupler and DIR compound of R-1 per mole of silver halide are the same as in Sample No. 103).
  • Sample No. 105 was prepared in the same manner as Sample No. 104 except for changing the emulsion contained in Sample No. 104 to EM-3.
  • the Samples Nos. 101 to 105 thus obtained were subjected to wedge exposure in conventional manner and processed according to the processing steps shown below.
  • gradation stability by processing, maximum density and sharpness (MTF value) were evaluated by performing sensitometry in conventional manner.
  • Table 4 shows the results of the green-sensitive layers.
  • Fig. 1 shows the characteristic curve which is the standard (broken line) and the characteristic curve (solid line) to be evaluated.
  • the absolute values A-y of the difference of the point gamma values at the respective exposure points of the characteristic curve which is the standard and the characteristic curve to be evaluated are determined.
  • the gradation stability is represented by the mean value of A-y multiplied by 1000 ( ⁇ ) and value of E of the standard deviation a of A-y multiplied by 1000.
  • the difference in point gammas between the both characteristics is greater as the value of ⁇ is greater, and the gradation change is not uniform indicating poor gradation stability as the value of ⁇ is greater.
  • the above standard is in the case of processing for 195 seconds, and the subject to be evaluated is the case of processing for 60 to 150 seconds.
  • Sample No. 105 contains an emulsion doped with Rh ions internally of the grains, the grain size distributions of the silver halide grains of the respective color sensitive layers are narrow, and therefore it is particularly preferable with respect to gradation stability.
  • the emulsion contained in Sample No. 105 has preferably high production efficiency, because physical aging and chemical aging can be effected each once in preparation of the emulsion.
  • the effects of the present invention could be recognized when the exemplary compounds (15), (19), (21), (20), (10) or (6) were used in place of the exemplary compound (1) represented by the formula (IS) in the color developing solution.
  • the samples used in the examples had the exposure latitude ( ⁇ log H) of 3.0 or more.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
EP19900301711 1989-02-21 1990-02-16 Méthode pour le traitement d'un matériau photosensible à halogénure d'argent pour photographie en couleurs Withdrawn EP0384670A3 (fr)

Applications Claiming Priority (2)

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JP4077889A JPH02220051A (ja) 1989-02-21 1989-02-21 ハロゲン化銀カラー写真感光材料の処理方法
JP40778/89 1989-02-21

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EP0384670A3 EP0384670A3 (fr) 1991-04-17

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0529992A1 (fr) * 1991-08-23 1993-03-03 Konica Corporation Matériau à halogénure d'argent pour photographie en couleurs
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

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2382028A1 (fr) * 1977-02-26 1978-09-22 Agfa Gevaert Ag Melange d'emulsions pour materiaux couleur inversibles (pour visionnage par reflexion)
EP0157146A2 (fr) * 1984-02-23 1985-10-09 Fuji Photo Film Co., Ltd. Matériau photographique en couleurs à l'halogénure d'argent, sensible à la lumière
GB2194068A (en) * 1985-07-01 1988-02-24 Fuji Photo Film Co Ltd Silver halide color photographic materials
EP0286403A2 (fr) * 1987-04-07 1988-10-12 EASTMAN KODAK COMPANY (a New Jersey corporation) Produits pour la photographie en couleur à l'halogénure d'argent

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2382028A1 (fr) * 1977-02-26 1978-09-22 Agfa Gevaert Ag Melange d'emulsions pour materiaux couleur inversibles (pour visionnage par reflexion)
EP0157146A2 (fr) * 1984-02-23 1985-10-09 Fuji Photo Film Co., Ltd. Matériau photographique en couleurs à l'halogénure d'argent, sensible à la lumière
GB2194068A (en) * 1985-07-01 1988-02-24 Fuji Photo Film Co Ltd Silver halide color photographic materials
EP0286403A2 (fr) * 1987-04-07 1988-10-12 EASTMAN KODAK COMPANY (a New Jersey corporation) Produits pour la photographie en couleur à l'halogénure d'argent

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0529992A1 (fr) * 1991-08-23 1993-03-03 Konica Corporation Matériau à halogénure d'argent pour photographie en couleurs
US5380639A (en) * 1991-08-23 1995-01-10 Konica Corporation Silver halide color photographic material
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

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EP0384670A3 (fr) 1991-04-17
JPH02220051A (ja) 1990-09-03

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