EP0598216A1 - Procédé de traitement de matériau photographique couleur à l'halogénure d'argent - Google Patents

Procédé de traitement de matériau photographique couleur à l'halogénure d'argent Download PDF

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Publication number
EP0598216A1
EP0598216A1 EP93116451A EP93116451A EP0598216A1 EP 0598216 A1 EP0598216 A1 EP 0598216A1 EP 93116451 A EP93116451 A EP 93116451A EP 93116451 A EP93116451 A EP 93116451A EP 0598216 A1 EP0598216 A1 EP 0598216A1
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Prior art keywords
group
silver halide
photographic material
formula
silver
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EP93116451A
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German (de)
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EP0598216B1 (fr
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Takatoshi C/O Fuji Photo Film Co. Ltd. Ishikawa
Hiroyuki C/O Fuji Photo Film Co. Ltd. Seki
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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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
    • G03C7/42—Bleach-fixing or agents therefor ; Desilvering processes

Definitions

  • This invention relates to a method for processing a silver halide color photographic material, and more particularly to a method for processing a silver halide color photographic material, which enables color restorability (dye reciprocity) to be greatly improved even through rapidly processed, and moreover which markedly prevents dyes from being faded by heat and prevents color stain.
  • Color developing solutions containing aromatic primary amine color developing agents have been conventionally used to form a color image, and play a leading role in color image formation.
  • the color developing solutions have a problem in that they are easily oxidized by air and metals. It is well known that when a color image is formed by using the oxidized developing solutions, fog is increased and sensitivity and gradation are fluctuated, and hence desired photographic characteristics can not be obtained.
  • an improvement in the problem of color stain greatly depends on the types of the bleaching agents, and it is required that fogging is not caused with time even when the stability of rinsing solutions is improved and bleaching components remain in the photographic materials. Further, the improvement in the problem of color stain greatly depends on the types of couplers used.
  • Rapid processing i.e., shortening of the processing time
  • the bleaching step in the desilverization stage includes so-called a color restoration stage wherein not only silver is oxidized, but also leuco ion dye is oxidized, thereby forming a cyan dye.
  • a color restoration stage wherein not only silver is oxidized, but also leuco ion dye is oxidized, thereby forming a cyan dye.
  • oxidation proceeds insufficiently so that lowering of the maximum density of cyan color, that is, a failure in color restoration is caused.
  • the bleaching-fixing bath or a prebath thereof has been proposed for enhancing the bleaching power, such as ammonium bromide described in JP-A-51-87036 (the term “JP-A” as used herein means an "unexamined published Japanese patent application”), water-soluble iodides described in U.K. Patent 926,569 and halides described in JP-B-53-11854 (the term “JP-B” as used herein means an "examined Japanese patent publication”).
  • Couplers described in JP-B-49-11572 and JP-A-59-166956 are known as cyan couplers capable of inhibiting color fading. Some of these couplers are expected to improve color restorability. However, the effect is not sufficient.
  • An object of the present invention is to provide a method for processing a silver halide color photographic material, which greatly improves the problems of color stain, color fading by heat and color restorability.
  • the above-described object of the present invention has been achieved by the method for processing a silver halide color photographic material which comprises processing a silver halide color photographic material containing at least one cyan coupler represented by formula (I) with a bath having a bleaching ability and containing at least one iron (III) complex of compounds represented by formula (II) after color development:
  • R a represents an alkyl group, a cycloalkyl group, an aryl group, an amino group or a heterocyclic group
  • R b represents an acylamino group or an alkyl group having at least 2 carbon atoms
  • R c represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group; or R c and R b may be combined together to form a ring
  • Z a represents a hydrogen atom, a halogen atom or a group which is eliminated by the reaction with an oxidation product of aromatic primary amine developing agents, wherein R1, R2, R3,
  • the alkyl group represented by R a is preferably an alkyl group having 1 to 32 carbon atoms.
  • the alkyl group include methyl group, butyl group, tridecyl group, cyclohexyl group and allyl group.
  • the aryl group represented by R a include phenyl group and naphthyl group.
  • a typical example of the heterocyclic group represented by R a includes 2-pyridyl group.
  • the groups represented by R a may be substituted by one or more substituents selected from the group consisting of an alkyl group, an aryl group, an alkyl-or aryloxy group (e.g., methoxy, dodecyloxy, methoxyethoxy, phenyloxy, 2,4-di-t-amylphenoxy, 3-t-buty-4-hydroxyphenyloxy, and naphthyloxy), a carboxy group, an alkyl- or arylcarbonyl group (e.g., methoxycarbonyl, and phenoxycarbonyl), an acyloxy group (e.g., acetyl, and benzoyloxy), a sulfamoyl group (e.g., N-ethylsulfamoyl, and N-octadecylsulfamoyl), a carbamoyl group (e.g., N-ethylcarbamoyl
  • Z a is a hydrogen atom, a halogen atom or a group which is eliminated by the reaction with an oxidation product of the aromatic primary amine color developing agents (an eliminable group).
  • the eliminable group and the halogen atom are collectively referred to as "coupling-eliminable group" (which is eliminated upon the coupling reaction with the oxidation product).
  • Examples of the coupling-eliminable group include a halogen atom (e.g., fluorine atom, chlorine atom, and bromine atom), an alkoxy group (e.g., dodecyloxy, methoxycarbamoylmethoxy, carboxypropyloxy, and methylsulfonylethoxy), an aryloxy group (e.g., 4-chlorophenoxy, and 4-methoxyphenoxy), an acyloxy group (e.g., acetoxy, tetradecanoyloxy, and benzoyloxy), a sulfonyloxy group (e.g., methanesulfonyloxy, and toluenesulfonyloxy), an amido group (e.g., dichloroacetylamino, methanesulfonylamino, toluenesulfonylamino), an alkoxycarbonyloxy group (e.g.
  • R b is an acylamino group or an alkyl group having at least 2 carbon atoms (e.g., ethyl, propyl, and t-butyl)
  • R c is a hydrogen atom, a halogen atom (e.g., fluorine atom, chlorine atom, and bromine atom), an alkyl group (e.g., methyl, ethyl, and propyl) or an alkoxy group (e.g., methoxy, and ethoxy), or R b and R c may be combined together to form a ring.
  • cyan couplers of formula (I) include the following compounds, but the present invention is not limited thereto.
  • the cyan couplers of formula (I) can be synthesized by the methods described in JP-A-59-166956 and JP-B-49-11572.
  • the amount of the cyan coupler of the present invention to be contained in the photographic material is not particularly limited, it is preferably from 1 ⁇ 10 ⁇ 6 to 1 ⁇ 10 ⁇ 2 mol, more preferably 1 ⁇ 10 ⁇ 5 to 1 ⁇ 10 ⁇ 3 mol per m2 of the photographic material.
  • the aliphatic group represented by R1, R2, R3, R4, R5 and R6 in formula (II) is preferably a straight chain, branched or cyclic alkyl, alkenyl or alkynyl group having up to 10 carbon atoms. More preferably, the aliphatic group is an alkyl group having 1 to 4 carbon atoms. Particularly preferred are methyl group and ethyl group.
  • the aromatic group represented by R1, R2, R3, R4, R5 and R6 is preferably a monocyclic or bicyclic aryl group.
  • Examples of the aryl group include phenyl group and naphthyl group. Phenyl group is more preferred.
  • the aliphatic group and the aromatic group represented by R1, R2, R3, R4, R5 and R6 may be substituted by one or more substituent groups such as an alkyl group (e.g., methyl, and ethyl), an aralkyl group (e.g., phenylmethyl), an alkenyl group (e.g., allyl), an alkynyl group, an alkoxy group (e.g, methoxy, and ethoxy), an aryl group (e.g., phenyl, and p-methylphenyl), an amino group (e.g., dimethylamino), an acylamino group (e.g., acetylamino), a sulfonylamino group (e.g., methanesulfonylamino), a ureido group, a urethane group, an aryloxy group (e.g., phenyloxy), a sulf
  • the number of carbon atoms contained therein is preferably 1 to 4.
  • R1, R2, R3, R4, R5 and R6 are each preferably a hydrogen atom or a hydroxy group, more preferably a hydrogen atom.
  • W is a bonding group represented by formula (W): -(W1-Z) n -W2- (W)
  • W1 is an alkyl group or a single bond.
  • the alkylene group represented by W1 is preferably a straight chain or branched alkylene group having 1 to 8 carbon atoms (e.g., methylene, ethylene, and propylene) or a cycloalkylene group having 5 to 10 carbon atoms (e.g., 1,2-cyclohexylene).
  • W2 is an alkylene group or -CO-.
  • the alkylene group represented by W2 has the same meaning as the alkylene group represented by W1.
  • the alkylene groups represented by W1 and W2 may be the same or different or may be substituted.
  • substituent groups include those already described above in the definition of the substituent groups for R1.
  • Preferred examples of the substituent groups include an alkyl group, a hydroxy group and a carboxy group. More preferably, W1 and W2 are each an alkylene group having 1 to 3 carbon atoms, particularly preferably methylene group or ethylene group.
  • Z is a single bond, -O-, -S-, -CO- or -N(R W )-wherein R W is a hydrogen atom or an alkyl group which may be substituted.
  • substituent groups include those already described above in the definition of the substituent groups for R1.
  • Preferred examples of the substituent groups include a carboxy group, a phosphono group, a sulfo group, a hydroxy group and an amino group.
  • Z is a single bond.
  • n is preferably 1 or 2, more preferably 1.
  • W include the following groups. -CH2CH2CH2OCH2CH2--CH2CH2OCH2CH2OCH2CH2- -CH2CH2SCH2CH2--CH2CH2SCH2CH2SCH2CH2- Examples of the cation represented by M1, M2, M3 and M4 include an alkali metal ion (e.g., lithium, sodium, or potassium ion), an ammonium ion (e.g., ammonium or tetraethylammonium ion) and a pyridium ion.
  • alkali metal ion e.g., lithium, sodium, or potassium ion
  • an ammonium ion e.g., ammonium or tetraethylammonium ion
  • pyridium ion pyridium ion
  • the compounds of formula (II) which can be used in the present invention include the following compounds, but the present invention is not limited thereto.
  • the compounds of formula (II) can be synthesized by referring to the methods described in JP-A-63-199295 and JP-A-3-173857. As described in these patent specifications, the compounds of formula (II) used in the present invention can exist in optically isomeric forms ([R,R], [S,S], [S,R], [R,S]) (while some of the compounds may have the same structure in the [S,R] form and the [R,S] form).
  • the compound of formula (II) is audinarily synthesized in the form of mixture of the four optical isomers of [R,R], [S,S], [S,R], and [R,S], each being contained in an amount of about 25 %.
  • the isomer of [S,S] form is preferred for the improvement in color stain, color fading by heat and color restorability.
  • the compound of formula (II) which is predominantly a [S,S] optical isomer, for example, those synthesized from L-amino acids, such as compound (II-1).
  • the [S,S] optical isomer is also advantageous in view of environmetal pollution since it is not likely to decompose spontaneously even when discharged.
  • the [S,S] optical isomers can be selectively obtained by the above-mentioned method in which L-amino acids are used as a starting material to synthesize the corresponding product of formula (II), or by the method in which the mixture of the optical isomers is subjected to conventional separation using a commercially available column.
  • the former method is preferred and is economical.
  • the term "predominantly” or “selectively” used herein means that the [S,S] optical isomer is contained in the compound of formula (II) in the largest content among the four optical isomers, generally not less than 50 %, preferably not less than 70 %, more preferably 90% or more.
  • the compound of formula (II) may consist of 100 % of the [S,S] form.
  • the iron (III) complexes of the compounds of formula (II) used in the present invention can be prepared by mixing a ferric ion with the compounds of formula (II).
  • the complexes may be isolated as the iron (III) complexes of the chelating agents and used.
  • the complexes may be isolated in the form of a salt such as an ammonium salt, a sodium salt or a potassium salt.
  • the iron (III) complexes are generally used in an amount of 0.02 to 1.0 mol, preferably 0.04 to 0.5 mol per liter of the bath having a bleaching ability. It is preferred that an excess (about 10 to 20% excess) of the compounds of formula (II) in the free form in addition to the iron (III) complexes be present. Of the compounds of formula (II), compounds II-1, II-2, II-3, II-15, II-16 and II-17 are particularly preferred.
  • the bath having a bleaching ability used in the present invention may be any of bleaching bath and bleaching-fixing bath, to which the iron (III) complexes of the compounds of formula (II) can be added.
  • the compounds of formula (II) used in the present invention are used as builders in the field of detergents as described in JP-A-63-199295 and JP-A-3-173857. Hence, the compounds are known compounds and belong to polyaminocarboxylic acids. However, the compounds of formula (II) have not been used in photographic processing, and the iron (III) complexes of the compounds of formula (II) have an excellent effect as a bleaching agent in comparison with the iron (III) complexes of EDTA conventionally used.
  • the processing method of the present invention can be applied to any of silver halide color photographic materials, that is, any of color paper, etc. However, the processing method of the present invention can be particularly preferably applied to color paper.
  • Silver halide emulsions, other materials (additives, etc.), photographic constituent layers (layer arrangement, etc.), processing methods and processing additives described in the following patent specifications, particularly European Patent EP 0,355,660A2 (JP-A-1-107011) can be preferably applied to the photographic materials used in the present invention.
  • examples of cyan couplers which can be used together with the cyan couplers of formula (I) include diphenylimidazole cyan couplers described in JP-A-2-33144; 3-hydroxypyridine cyan couplers (particularly two equivalent type coupler obtained by introducing a chlorine eliminable group into a four equivalent type coupler designated as coupler (42); and couplers (6) and (9)) described in EP 0,333,185A2; and cyclic active methylene cyan couplers (particularly coupler Nos. 3, 8 and 34) described in JP-A-64-32260.
  • silver halides having a high silver chloride content are preferred. More specifically, silver chlorobromide containing substantially no silver iodide and having a silver chloride content of preferably at least 90 mol%, more preferably at least 95 mol%, particularly preferably at least 98 mol%, or silver chloride is preferred.
  • containing substantially no silver iodide used herein imply that the silver iodide content is not more than 1 mol% and preferably 0.5 mol% or less, and it may be 0 mol%.
  • the silver halide emulsion used in the present invention is preferably a monodisperse emulsion and more preferably that having a coefficient of variation of 0.2 % or less, particularly preferably 0.1 % or less.
  • dyes decolorized by processing are added to hydrophilic colloid layers of the photographic materials in such an amount as to provide an optical density of at least 0.70 at 680 nm, or that at least 12 wt% (more preferably at least 14 wt%) of titanium oxide having a surface treated with a dihydric to tetrahydric alcohol (e.g., trimethylol ethane) is contained in a water-resistant resin layer of the support.
  • a dihydric to tetrahydric alcohol e.g., trimethylol ethane
  • the photographic materials used in the present invention preferably contain dye image preservability improvers described in EP 0,277,589A2 together with the couplers, particularly pyrazoloazole couplers.
  • the photographic materials preferably contain a compound (F) and/or a compound (G), said compound (F) being chemically bonded to the aromatic amine color developing agent left behind after color development to form a compound which is chemically inert and substantially colorless, and said compound (G) being chemically bonded to an oxidation product of the aromatic amine color developing agent left behind after color development to form a compound which is chemically inert and substantially colorless.
  • the use of the compound (F) and/or the compound (G) is preferred from the standpoint of preventing stain from being formed by developed dyes produced by the reaction with the color developing agents or the oxidation product thereof left in the layers during storage after processing and preventing other side effects from being caused.
  • antifungal agents as described in JP-A-63-271247 are added to the photographic materials to prevent the image from being deteriorated by the growth of mildew or microbe in the hydrophilic layers.
  • supports for display which can be used for the photographic materials of the present invention include white polyester supports and supports having a white pigment-containing layer provided on the silver halide emulsion layer side thereof. It is preferred that an antihalation layer is coated on the silver halide emulsion layer-coated side of the support or the back side thereof. It is particularly preferred that the transmission density of the support is set to from 0.35 to 0.8 so as to allow display to be enjoyed by reflected light and transmitted light.
  • the coated amount of silver in the photographic material used in the present invention is preferably 1 g or less, more preferably from 0.4 to 0.8 g, particularly preferably from 0.5 to 0.7 g, per m2 of the photographic material.
  • the dry thickness of the entire photographic constituent layers is preferably from 6 to 11 ⁇ m.
  • the photographic materials of the present invention may be exposed to visible light or infrared light. Exposure may be any of low-illumination exposure and high-illumination short-time exposure. In the latter case, a laser scanning exposure system wherein the exposure time is shorter than 10 ⁇ 4 sec per one pixel is preferred.
  • the color developing solutions used in the development of the photographic materials in the present invention are preferably aqueous alkaline solutions containing aromatic primary amine color developing agents as principal ingredients.
  • Aminophenol compounds are useful as the color developing agents.
  • p-phenylenediamine compounds can be preferably used as the color developing agents.
  • Typical examples of the p-phenylenediamine compounds include 3-methyl-4-amino-N,N-diethylaniline, 4-amino-N-ethyl-N- ⁇ -hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -methoxyethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -hydroxybutylaniline and their sulfates, hydrochlorides and p-toluenesufonates. These compounds may be used in combination of two or more thereof according to purpose.
  • the color developing solutions contain pH buffering such as alkali metal carbonates, borates and phosphates and restrainers or anti-fogging agents such as bromides, iodides, benzimidazoles, benzthiazoles and mercapto compounds.
  • pH buffering such as alkali metal carbonates, borates and phosphates and restrainers or anti-fogging agents such as bromides, iodides, benzimidazoles, benzthiazoles and mercapto compounds.
  • the color developing solutions may optionally contain preservatives such as hydroxylamine, N,N-di(sulfoethyl)-hydroxylamine, diethylhydroxylamine, sulfites, hydrazines, phenylsemicarbazides, triethanolamine and catecholdisulfonic acids; organic solvents such as ethylene glycol and diethylene glycol; development accelerators such as benzyl alcohol, polyethylene glycol and quaternary ammonium salts; dye forming couplers; competitive couplers; fogging agents such as sodium boron hydride; auxiliary developing agents such as 1-phenyl-3-pyrazolidone; tackifiers; and various chelating agents such as typically aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids and phosphonocarboxylic acids, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid,
  • the replenishment rate of the color developing solution varies depending on the color photographic materials to be processed, but is generally one liter or less per m2 of the photographic material.
  • the replenishment rate can be reduced to 300 ml or less when the concentration of bromide ions in the replenisher is reduced.
  • the replenishment rate is preferably 30 to 150 ml/m2. It is preferred that when the replenishment rate is to be reduced, the contact area of the developing solution with air in the processing bath is decreased to thereby prevent the developing solution from evaporating or being oxidized by air. Further, the replenishment rate can be reduced by using a means for preventing bromide ions in the developing solution from being accumulated.
  • the photographic emulsion layers are bleached with a bath having a bleaching ability.
  • Bleaching and fixing may be simultaneously conducted (bleaching-fixing) or may be separately conducted.
  • bleaching-fixing may be carried out to expedite processing. Processing may be conducted by using a bleaching-fixing bath composed of two consecutive baths. Fixing may be conducted before bleaching-fixing, or after bleaching-fixing.
  • the iron (III) complexes of the compounds of formula (II) must be used as the bleaching agents as described above. If desired, other bleaching agents may be used together with the iron (III) complexes of the compounds of formula (II).
  • bleaching agents which can be used together with the iron (III) complexes of the compounds of formula (II) include ferricyanides; dichromates; organic complex salts of iron (III) or cobalt (III), for example, iron (III) or cobalt (III) complex salts of aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid and glycol ether diaminetetraacetic acid or organic acids such as citric acid, tartaric acid and malic acid; persulfates; bromates; permanganates; and nitrobenzenes.
  • aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic
  • the bleaching bath, the bleaching-fixing bath and the prebath thereof may optionally contain bleaching accelerators.
  • useful bleaching accelerators include compounds having a mercapto group or a disulfide bond described in U.S. Patent 3,893,858, West German Patent 1,290,812, JP-A-53-95630 and Research Disclosure No. 17,129 (July 1978); thiazolidine derivatives described in JP-A-50-140129; thiourea derivatives described in U.S Patent 3,706,561; iodides described in JP-A-58-16235; polyoxyethylene compounds described in West German Patent 2,748,430; polyamine compounds described in JP-B-45-8836; and bromide ions.
  • the compounds having a mercapto group or a disulfide bond are preferred from the standpoint of providing a high accelerating effect.
  • the compounds described in U.S. Patent 3,893,858, West German Patent 1,290,812 and JP-A-53-95630 are particularly preferred. Further, compounds described in U.S. Patent 4,552,834 are preferred.
  • These bleaching accelerators may be added to the photographic materials.
  • the bleaching accelerators are particularly effective in conducting the bleaching-fixing of the color photographic materials for photographing.
  • the processing time with the bath having a bleaching ability is preferably 15 to 60 seconds, more preferably 20 to 50 seconds from the standpoint of rapid processing. When the processing time is too short, a failure in desilverization occurs and the effect of the present invention can be hardly obtained.
  • the replenishment rate of the bleaching or bleaching-fixing solution is generally one liter or less, preferably 300 ml or less, more preferably from 30 to 150 ml, per m2 of the photographic material.
  • Bleaching components and fixing components may be separately replenished so as to avoid problems with respect to stability and crystallization of the components in the replenisher.
  • fixing agents include thiosulfates, thiocyanates, thioether compounds, thioureas and many iodides.
  • Thiosulfates are generally used. Particularly, ammonium thiosulfate is most widely used.
  • preservatives which can be preferably used in the bleaching-fixing solution and the fixing solution include sulfites, bisulfites, benzenesulfonic acids and carbonyl bisulfite adducts.
  • the silver halide color photographic materials are generally subjected to the rinsing stage and/or the stabilizing stage.
  • the amount of rinsing water in the rinsing stage widely varies depending on the characteristics (e.g., materials used such as couplers used) and use of the photographic materials, the temperature of rinsing water, the number of rinsing tanks (the number of stages), replenishment system (countercurrent or direct flow), other conditions.
  • the relationship between the number of rinsing tanks and the amount of rinsing water in a multi-stage countercurrent system can be determined by the method described in Journal of the Society of Motion Picture and Television Engineers , No. 64, pages 248 to 253 ( May 1955).
  • the amount of rinsing water can be greatly reduced.
  • the residence time of water in the tank is prolonged, there is caused a problem that bacteria are grown and suspended matters formed are deposited on the photographic materials.
  • the method for reducing calcium ion and magnesium ion described in JP-A-62-288838 can be very effectively used as a means for solving the problem in the processing of the color photographic materials. Further, antibacterial agents and antifungal agents described hereinafter can be added.
  • the pH of rinsing water in the processing of the photographic materials of the present invention is 4 to 9, preferably 5 to 8.
  • the temperature of rinsing water and the rinsing time can be widely varied depending on the characteristics and use of the photographic materials.
  • the temperature of rinsing water and the rinsing time in the present invention are 15 to 45°C for 10 sec to 2 min, preferably 25 to 40°C for 20 to 90 sec.
  • the photographic materials may be processed directly with a stabilizing solution in place of rinsing water in the present invention. All of conventional methods described in JP-A-57-8543, JP-A-58-14834 and JP-A-60-220345 can be used in the stabilization stage.
  • rinsing water and the stabilizing solution contain various surfactants to prevent water spots from being formed during the drying of the photographic materials after processing.
  • the surfactants include polyethylene glycol type nonionic surfactants, polyhydric alcohol type nonionic surfactants, alkylbenzenesulfonate type anionic surfactants, higher alcohol sulfuric ester salt type anionic surfactants, alkylnaphthalenesulfonate type anionic surfactants, quaternary ammonium salt type cationic surfactants, amine salt type cationic surfactants, amine salt type ampholytic surfactants and betaine type ampholytic surfactants. Of these surfactants, nonionic surfactants are preferred.
  • ethylene oxide adducts of alkylphenols are particularly preferred as the alkylphenols.
  • Octyl-, nonyl-, dodecyl- and dinonylphenols are particularly preferred as the alkylphenols.
  • the number of moles of the addition of ethylene oxide is preferably 8 to 14. It is also preferred that silicone surfactants having a high anti-foaming effect are used.
  • rinsing water and the stabilizing solution contain various antibacterial agents and antifungal agents to prevent fur from forming and to prevent mold from growing on the photographic materials.
  • antibacterial agents and the antifungal agents include thiazolylbenzimidazole compounds described in JP-A-57-157244 and JP-A-58-105145, isothiazolone compounds described in JP-A-57-8542, chlorophenol compounds such as typically trichlorophenol, bromophenol compounds, organotin compounds, organozinc compounds, acid amide compounds, diazine and triazine compounds, benztriazole compounds, alkylguanidine compounds, quaternary ammonium salts such as typically benzaluminium chloride, antibiotics such as typically penicillin and general-purpose antifungal agents described in J. Antibacterial and Anti-fungus Agents , Vol. 1, No. 5, pp. 207-223 (1983). These agents may be used in combination of two or more of them. Further, various microbicides, thi
  • rinsing water and the stabilizing solution contain chelating agents.
  • the chelating agents which can be preferably used include aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, organic phosphonic acids such as 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetraacetic acid, and diethylenetriamine-N,N,N',N'-tetramethylenephosphonic acid, and the hydrolyzates of maleic anhydride polymers described in European Patent 345,172A1.
  • the stabilizing solution contains compounds capable of stabilizing the dye image such as formalin, hexamethylenetetramine and derivatives thereof, hexahydrotriazine and derivatives, dimethylol urea and N-methylol compounds such as N-methylol pyrazole, organic acids and pH buffering agents. These compounds are used in an amount of preferably 0.001 to 0.02 mol per liter of the stabilizing solution. It is preferred that the concentration of free formaldehyde is as low as possible because the evolution of formaldehyde gas is reduced. From this point of view, hexamethylenetetramine, N-methylol azoles such as N-methylol pyrazole described in Japanese Patent Application No.
  • Hei 3-318644 and azolylmethylamines such as N,N'-bis(1,2,4-triazole-1-yl)-piperazine described in JP-A-4-313753 are preferred as dye image stabilizers.
  • the stabilizing solution optionally contains ammonium compounds such as ammonium chloride and ammonium sulfite, metallic (e.g., Bi, Al) compounds, fluorescent brighteners, hardening agents, alkanolamines (described in U.S. Patent 4,786,583) and preservatives which can be contained in the bleaching solution and the bleaching-fixing solution.
  • sulfinic acid compounds e.g., benzenesulfinic acid, toluenesulfinic acid or sodium or potassium salt thereof
  • sulfinic acid compounds are preferred. These compounds are used in an amount of preferably 1 ⁇ 10 ⁇ 5 to 1 ⁇ 10 ⁇ 3 mol, particularly preferably 3 ⁇ 10 ⁇ 5 to 5 ⁇ 10 ⁇ 4 mol per liter of the stabilizing solution.
  • the replenishment rate of the rinsing water and the stabilizing solution is preferably low and it is desirably within the range of 0.1 to 50 times, more preferably 3 to 30 times, the amount thereof carried out with the unit area of the photographic material into the pre-bath.
  • various processing solutions are used at a temperature of 10 to 50°C. Usually, a temperature of 33 to 42°C is used. However, it is possible that a higher temperature is used to accelerate processing and to shorten the processing time, while a lower temperature is used to improve image quality and the stability of the processing solutions. If desired, treatments using cobalt intensification or hydrogen peroxide intensification described in West German Patent 2,226,770 and U.S. Patent 3,674,499 may be carried out to save silver of the photographic materials.
  • Both sides of a paper support were laminated with polyethylene.
  • the surface of the support was subjected to a corona discharge treatment.
  • a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided thereon.
  • the following photographic constituent layers were coated thereon to prepare a multi-layer color photographic paper having the following layer structure. Coating solutions were prepared in the following manner.
  • the resulting solution was emulsified and dispersed in 500 cc of a 20% aqueous gelatin solution containing 8 cc of sodium dodecylbenzenesulfonate by using an ultrasonic homogenizer to prepare an emulsified dispersion.
  • a silver chlorobromide emulsion (cubic; a 1:4 (by Ag mol) mixture of a larger-size emulsion having a mean grain size of 0.58 ⁇ m and a smaller-size emulsion having a mean grain size of 0.45 ⁇ m; a coefficient of variation in a grain size distribution being 0.09 and 0.11, respectively; 0.6 mol% of AgBr being localized on a part of the surface of the grain in each size emulsion) was prepared.
  • red-sensitive sensitizing dye E 0.9 ⁇ 10 ⁇ 4 mol was added to the larger-size emulsion, and 1.1 ⁇ 10 ⁇ 4 mol was added to the smaller-size emulsion, each amount being per mol of silver.
  • the chemical ripening of the emulsion was carried out by adding a sulfur sensitizing agent and a gold sensitizing agent.
  • the above emulsified dispersion and the red-sensitive silver chlorobromide emulsion were mixed and dissolved, and a coating solution for the fifth layer was prepared so as to give the composition as described later.
  • Coating solutions for the first through fourth layers, the sixth layer and the seventh layer were prepared in the same manner as in the preparation of the coating solution for the fifth layer as described above.
  • Sodium salt of 1-oxy-3,5-dichloro-s-triazine was used as a hardening agent for gelatin in each layer. Further, Cpd-10 and Cpd-11 were added to each layer in such an amount as to give 25.0 mg/m2 and 50.0 mg/m2 in total, respectively.
  • the following spectral sensitizing dyes were used in the silver chlorobromide emulsion of each light-sensitive emulsion layer.
  • the following dyes (parenthesized numerals being coating weights) were added to the emulsion layers.
  • Each layer had the following composition.
  • Numerals represent coating weights (g/m2).
  • the amount of silver halide emulsion is represented by the coating weight in terms of silver.
  • Polyethylene-laminated paper [Polyethylene on the first layer side contained a white pigment (TiO2) and bluish dye (Ultramarine)]
  • Silver Chlorobromide Emulsion (cubic; a 3:7 (by Ag mol) mixture of a larger-size emulsion having a mean grain size of 0.88 ⁇ m and a smaller-size emulsion having a mean grain size of 0.70 ⁇ m; a coefficient of variation in grain size distribution being 0.08 and 0.10, respectively; 0.3 mol% of silver bromide being localized on a part of the surface of the grain in each size emulsion) 0.30 Gelatin 1.86 Yellow Coupler (ExY) 0.82 Dye Image Stabilizer (Cpd-1) 0.19 Solvent (Solv-3) 0.18 Solvent (Solv-7) 0.18 Dye Image Stabilizer (Cpd-7) 0.06
  • Silver Chlorobromide Emulsion (cubic; a 1:3 (by Ag mol) mixture of a larger-size emulsion having a mean grain size of 0.55 ⁇ m and a smaller-size emulsion having a mean grain size of 0.39 ⁇ m; a coefficient of variation in a grain size distribution being 0.10 and 0.08, respectively; 0.8 mol% of silver bromide being localized on a part of the surface of the grain in each size emulsion) 0.12 Gelatin 1.24 Magenta Coupler (ExM) 0.23 Dye Image Stabilizer (Cpd-2) 0.03 Dye Image Stabilizer (Cpd-3) 0.16 Dye Image Stabilizer (Cpd-4) 0.02 Dye Image Stabilizer (Cpd-9) 0.02 Solvent (Solv-2) 0.40
  • UV-1 Ultraviolet Light Absorber
  • Cpd-5 Color Mixing Inhibitor
  • Solv-5 Solvent
  • Silver Chlorobromide Emulsion (cubic; a 1:4 (by Ag mol) mixture of a larger-size emulsion having a mean grain size of 0.58 ⁇ m and a smaller-size emulsion having a mean grain size of 0.45 ⁇ m; a coefficient of variation in a grain size distribution being 0.09 and 0.11, respectively; 0.6 mol% of silver bromide being localized on a part of the surface of the grain in each size emulsion) 0.23 Gelatin 1.34 Cyan Coupler (ExC) 0.32 Dye Image Stabilizer (Cpd-2) 0.03 Dye Image Stabilizer (Cpd-4) 0.02 Dye Image Stabilizer (Cpd-6) 0.18 Dye Image Stabilizer (Cpd-7) 0.40 Dye Image Stabilizer (Cpd-8) 0.05 Solvent (Solv-6) 0.14
  • UV-1 Ultraviolet Light Absorber
  • Cpd-5 Color Mixing Inhibitor
  • Solv-5 Solvent
  • UV-1 Ultraviolet Light Absorber
  • sample 1-A The photographic material prepared above is referred to as sample 1-A.
  • ExampleC cyan couplers
  • Sample 1-B The following cyan coupler Sample 1-C: cyan coupler (C-1)
  • Sample 1-D cyan coupler (C-2)
  • Sample 1-E cyan coupler (C-9)
  • Each of the above samples was subjected to a running test.
  • the photographic materials were imagewise exposed to light by using an automatic printer FAP3500 (a product of Fuji Photo Film Co., Ltd.), and continuously processed (continuous test) in the following stages with the following processing solutions until the amount of the replenisher of the bleaching-fixing solution reached twice the amount of the tank solution.
  • FAP3500 a product of Fuji Photo Film Co., Ltd.
  • the compound capable of forming the iron (III) complex (bleaching agent) in the composition of the bleaching-fixing solution was changed as shown in Table 1 below.
  • Each processing solution had the following composition.
  • Ion-exchanged water the concentration of each of calcium ion and magnesium ion was reduced to 3 ppm or lower.
  • each sample was subjected to gradation exposure through a filter for sensitometry at the time of the start of running and at the time of the end thereof by using a sensitometer (FWH type, the color temperature of light source: 3200°K, a product of Fuji Photo Film Co., Ltd.) (the exposure to light was made such that the exposure time was 0.1 sec and an exposure amount of 250 CMS was given).
  • the exposed samples were processed.
  • the density of each of the processed samples was measured with an autographic densitometer, and a difference ( ⁇ D Bmin ) in the change of the minimum density of yellow density in the unexposed area between the start of the running and the end thereof was determined.
  • the maximum density area was immersed in a bleaching solution for color negative films (CN-16X N2 bleach, a product of Fuji Phofo Film Co., Ltd.) for 4 minutes, rinsed and dried, and the cyan density was re-measured.
  • the ratio of an increase in the maximum cyan density (a degree of a failure in color restoration) was referred to as color development ratio P(%).
  • an increase in yellow stain on the white ground is small, and at the same time, the fading of cyan color and a failure in color restoration are reduced. Accordingly, it can be found that good results can be obtained by the processing method of the present invention.
  • the fading of cyan color and the failure in color restoration can be further reduced when compounds II-1 and II-2 each predominantly composed of a [S,S] optical isomer are used as in Run No. 1-8 and 1-9, respectively.
  • color stain and the fading of cyan color can be reduced and good results can be obtained particularly when the bleaching-fixing time is 15 to 60 sec.
  • Sample 1-C prepared in Example 1 was subjected to a running test.
  • the photographic materials were imagewise exposed to light by using an automatic printer FAP3500 (a product of Fuji Photo Film Co., Ltd.), and continuously processed (continuous test) in the following stages with the following processing solutions until the amount of the replenisher of the bleaching solution reached three times the amount of the tank solution.
  • the compound capable of forming the iron (III) complex (bleaching agent) in the composition of the bleaching solution was changed as shown in Table 3 below.
  • Each processing solution had the following composition.
  • Tank Solution Replenisher Water 600 ml 600 ml 1-Hydroxyethylidene-1,1-diphosphonic acid (60%) 2.0 g 2.0 g Triethanolamine 14.0 g 14.0 g Lithium Sulfate 1.0 g 1.0 g Diethylhydroxyamine 3.0 g 4.0 g Sodium Chloride 3.0 g - N-Ethyl-N-( ⁇ -methanesulfonamidoethyl)-3-methyl-4-aminoaniline Sulfate 4.0 g 8.5 g Fluorescent Brightener (UNITEX-CK, a product of Cibu-Geigy AG) 1.5 g 3.0 g Potassium Carbonate 27 g 27 g Water to make 1000 ml 1000 ml pH (adjusted with KOH) 10.0 10.0 10.0
  • Tank Solution Replenisher Water 600 ml 600 ml Ammonium Thiosulfate 100 g 110 g Ammonium Sulfite 15 g 20 g EDTA 2Na 2 g 2 g Water to make 1000 ml 1000 ml pH 7.0 7.3
  • each sample was subjected to gradation exposure through a filter for sensitometry at the time of the start of running and at the time of the end thereof by using a sensitometer in the same manner as in Example 1.
  • the exposed samples were processed.
  • the properties ( ⁇ D Bmin , ⁇ D Rmax and P) of each of the pocessed samples were measured, and the results are shown in Table 3.
  • the samples as processed according to the present invention exhibited minimized yellow stain and fading of cyan color and a reduced failure in color restoration.
  • the processing method of the silver halide color photographic material of the present invention provides excellent effect that color restoration can be improved with a high color restoration ratio, the dyes can be remarkably prevented from being faded by heat, and color staining can be prevented from occurring, even though rapid processing is conducted.
  • These effects can be further enhanced by the use of the compound of formula (II) which is predominantly a [S,S] optical isomer.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
EP19930116451 1992-10-15 1993-10-11 Procédé de traitement de matériau photographique couleur à l'halogénure d'argent Expired - Lifetime EP0598216B1 (fr)

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JP301571/92 1992-10-15
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10752640B2 (en) 2014-08-01 2020-08-25 Nuevolution A/S Compounds active towards bromodomains

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0121365A2 (fr) * 1983-03-14 1984-10-10 Fuji Photo Film Co., Ltd. Matériau photographique couleur à l'halogénure d'argent sensible à la lumière
US4983315A (en) * 1989-08-10 1991-01-08 The Procter & Gamble Company N,N'-(1-oxo-1,2-ethanediyl)-bis(aspartic acid), salts and use in detergent compositions
EP0430000A1 (fr) * 1989-12-01 1991-06-05 Agfa-Gevaert AG Bain de blanchissement
EP0532003A1 (fr) * 1991-09-11 1993-03-17 Konica Corporation Solution de traitement pour un matériau photographique couleur à l'halogénure d'argent sensible à la lumière
EP0553569A1 (fr) * 1991-12-27 1993-08-04 Konica Corporation Procédé de traitement de matériaux photographiques couleur à l'halogénure d'argent sensible à la lumière
EP0556782A1 (fr) * 1992-02-17 1993-08-25 Konica Corporation Solution de blanchiment ou de blanchiment-fixage et méthode de traitement de matériaux photographiques couleur à l'halogénure d'argent sensibles à la lumière utilisant cette solution
EP0567126A1 (fr) * 1992-04-24 1993-10-27 Fuji Photo Film Co., Ltd. Composition de traitement pour un produit photographique à l'halogénure d'argent et méthode de traitement l'utilisant

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0121365A2 (fr) * 1983-03-14 1984-10-10 Fuji Photo Film Co., Ltd. Matériau photographique couleur à l'halogénure d'argent sensible à la lumière
US4983315A (en) * 1989-08-10 1991-01-08 The Procter & Gamble Company N,N'-(1-oxo-1,2-ethanediyl)-bis(aspartic acid), salts and use in detergent compositions
EP0430000A1 (fr) * 1989-12-01 1991-06-05 Agfa-Gevaert AG Bain de blanchissement
EP0532003A1 (fr) * 1991-09-11 1993-03-17 Konica Corporation Solution de traitement pour un matériau photographique couleur à l'halogénure d'argent sensible à la lumière
EP0553569A1 (fr) * 1991-12-27 1993-08-04 Konica Corporation Procédé de traitement de matériaux photographiques couleur à l'halogénure d'argent sensible à la lumière
EP0556782A1 (fr) * 1992-02-17 1993-08-25 Konica Corporation Solution de blanchiment ou de blanchiment-fixage et méthode de traitement de matériaux photographiques couleur à l'halogénure d'argent sensibles à la lumière utilisant cette solution
EP0567126A1 (fr) * 1992-04-24 1993-10-27 Fuji Photo Film Co., Ltd. Composition de traitement pour un produit photographique à l'halogénure d'argent et méthode de traitement l'utilisant

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10752640B2 (en) 2014-08-01 2020-08-25 Nuevolution A/S Compounds active towards bromodomains

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