EP0410450B1 - Procédé de traitement de matériaux photographiques couleur à l'halogénure d'argent - Google Patents

Procédé de traitement de matériaux photographiques couleur à l'halogénure d'argent Download PDF

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Publication number
EP0410450B1
EP0410450B1 EP19900114363 EP90114363A EP0410450B1 EP 0410450 B1 EP0410450 B1 EP 0410450B1 EP 19900114363 EP19900114363 EP 19900114363 EP 90114363 A EP90114363 A EP 90114363A EP 0410450 B1 EP0410450 B1 EP 0410450B1
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Prior art keywords
color
silver halide
mol
group
silver
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German (de)
English (en)
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EP0410450A3 (en
EP0410450A2 (fr
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Koichi Fuji Photo Film Co. Ltd. Nakamura
Nobutaka Fuji Photo Film Co. Ltd. Ohki
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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
    • G03C7/407—Development processes or agents therefor
    • G03C7/413—Developers
    • G03C7/4136—Developers p-Phenylenediamine or derivatives thereof

Definitions

  • the present invention relates to a process for developing a color photographic light-sensitive material comprising photosensitive silver halides and color couplers (e.g., color photographic papers). More particularly, the present invention relates to a fast color development process suitable for stable processing and capable of giving images having a high color image stability.
  • Processing for silver halide color photographic materials comprises three basic steps including developing (in the case of the development for color reversal materials, a black-and-white (or first) development is employed before color development), desilvering, and washing.
  • the desilvering step is composed of a bleach step and a fixing step or a mono- bath bleach-fixing ("blix") step which includes both bleaching and fixing.
  • additional processing steps can be used, such as a stabilizing step, a prebath processing step before each processing step and a stop-bath processing step can be employed as is determined to be most suitable.
  • JP-A-58-95345, JP-A-59-232342 and JP-A-61-70552 the term "JP-A” as used herein refers to a "published unexamined Japanese patent application” and WO 87-04534, and this method is considered to be an effective means of enabling fast processing with low amounts of replenisher used with the developer.
  • the aforesaid method suffers from the problem of difficulty in attaining very fast processing times (e.g., within 30 seconds) while maintaining stable color development and ensuring stable photographic developing during continuous processing using conventional color developing agents, such as, e.g., 4-amino-3-methyl-N-ethyl-N-[3-meth- anesulfonamidoethylaniline salt.
  • conventional color developing agents such as, e.g., 4-amino-3-methyl-N-ethyl-N-[3-meth- anesulfonamidoethylaniline salt.
  • silver halide photographic materials e.g., having a high silver chloride content
  • the processing speed can be increased, but the resulting stability of both the processing solution and that of the developed photographic material are so reduced as to render this method of processing unsuitable for any practical or commercial use.
  • JP-A-61-261740 corresponding to EP-A-202616, JP-A-61-275837 and EP-A-269740 disclose the use of N-hydroxyalkyl-substituted p-phenylenediamine derivaties as a color developing agent, in order to inhibit undesirable variation in the photographic performance, due to the presence of accumulated bromide ion, when silver halide photographic materials are developed that comprise silver halides having mostly silver chlorobromide.
  • the specifications cited above describe improvement of storage stability of formed color images by carrying out the color development in a short time in order to reduce the amount of the color developing agent remaining in the silver halide photographic materials.
  • the rate of color development varies according to which type p-phenylenediamine derivative is used as a component of the developing agent.
  • a color developing agent having a hydrophobic group at the N-substituted position such as a 4-amino-3-methyl-N,N-diethylaniline salt and a 4-amino-3-methyl-N-ethyl-N-methoxyethyl- aniline salt, is readily distributed with a coupler or other developer components into an oil drop phase of a photographic material, in order to increase the rate of developing reactions.
  • a color developing agent has been used for faster development. Examples of such developing agents and how they are made are disclosed in U.S. Patents 3,656,905, 3,656,925 and 4,035,188.
  • a fast method of color development has been employed using a color developing agent having a hydrophilic group at the N-substituted position, such as a 4-amino-3-methyl-N-ethyl-N-(3-methanesulfonamidoethyl- aniline salt and a 4-amino-3-methyi-N-ethyi-N-p-hydroxyethyianiiine salt.
  • a developer additionally contains benzyl alcohol, in order to accelerate the distribution of the color developing agent in the oil drop phases of a color photographic light-sensitive material.
  • an object of the present invention to provide a method for continuous processing of color photographic light-sensitive material which provides a developed photographic material having extended color fastness or stability, suitable for long storage, and additionally provides for fast development using relatively short periods of time in a developer, while producing reduced or no color developer waste.
  • a method for developing an imagewise exposed silver halide color photographic material which comprises developing a color photographic material containing silver halide grains in a silver halide emulsion, said emulsion comprising (i) less than 1 mol% silver iodide and (ii) at least 80 mol% silver chloride, with a developer comprising (i) less than 2 ml/I benzyl alcohol and (ii) a p-phenylenediamine derivative represented by the formula (I): wherein R 1 and R 3 each represents an alkyl group having from 1 to 4 carbon atoms and R 2 represents a straight chain or branched alkylene group having 3 or 4 carbon atoms and wherein said developing is conducted in a period of time of 30 seconds or less, preferably 20 seconds or less, and preferably at a temperature of at least 30°C.
  • Another embodiment of the present invention provides an amount of replenisher for a color developer that is not more than about 120 ml, and preferably from about 15 to 60 ml per square meter of the color photographic material.
  • the above described developing process is carried out without using replenishers (however, water lost by evaporation can be replenished according to the present invention).
  • Developing time in this context, refers to a period of time during which the color photographic material retains in contact with the bulk of a color developer.
  • the first factor is that a color developing agent is rapidly supplied to the lowermost emulsion layer of a color photographic material. That is, a color developing agent which is reluctant to be trapped in oil drop phases and which has a high diffusion rate is used.
  • a developing agent having a hydrophilic group is preferably used. Also, it is preferred that benzyl alcohol accelerating the distribution of a color developing agent into oil drop phases is not used.
  • a second factor is that a color developing agent having a hydrophilic group and a high reducing power is used in order to enhance developability.
  • the development activity of, for example, a 4-amino-3-methyt-N-ethyt-N-p-meth- anesulfonamidoethylaniline salt, which is used for processing color photographic papers at present can be increased to be used in the method of the present invention by replacing the N-methanesulfonamido group of the salt with an N-hydroxyalkyl group Such a replacement increases hydrophilic properties as a developer and, at the same time, increases its reducing power. But, the reduction of the light fastness of color images formed is unavoidable, as described above.
  • a compound having a straight chain or branched alkylene group having 5 or more carbon atoms as R 2 is inferior in the light fastness of colored images and greatly inferior in fast processing, to such a compound, used in the method of the present invention, having a straight chain or branched alkylene group having 3 or 4 carbon atoms as R 2 .
  • magenta color images it has also been found that in the fast color development process of the present invention the storage stability of the color images are more greatly improved and the stain formation caused by storage can be more significantly inhibited with 2-equivalent couplers having an anion-releasing group introduced at a coupling position than with the conventional 5-pyrazolone based 4-equivalent couplers. It has also been found that preferably a pyrazoloazole based magenta coupler, particularly preferably a magenta coupler represented by formula (M-II) described hereinbelow can be used to obtain an image having a still further improved long term storage stability in a very fast development process.
  • M-II magenta coupler represented by formula
  • a color developing agent used in the method of the present invention is represented by the following formula (I), as described above, as follows: wherein R 1 and R 3 each represents an alkyl group having from 1 to 4 carbon atoms and R 2 represents a straight chain or branched alkylene group having 3 or 4 carbon atoms.
  • alkyl group shown by R 1 and R 3 include methyl, ethyl, propyl, isopropyl, butyl, and sec-butyl.
  • specific examples of the alkylene group shown by R 2 include propylene, butylene, 1-methylethylene, 2-methylethylene, 1-methylpropylene, 2-methylpropylene, and 3-methylpropylene.
  • R 1 represents preferably ethyl or propyl
  • R 3 represents preferably methyl or ethyl
  • R 2 represents preferably propylene or butylene as a main chain, and most preferably butylene.
  • a compound shown by formula (I) is very unstable in the case of storing the compound as a free amine and hence it is preferred that such a compound be generally stored as a salt of an inorganic acid or an organic acid and is used as a free amine, e.g., by adding such a compound to a color developer.
  • Examples of an inorganic acid and organic acid forming a salt of a compound of formula (I) include hydrochloric acid, sulfuric acid, phosphoric acid, p-toluenesulfonic acid, methanesulfonic acid, and naphthalene-1,5-disulfonic acid.
  • the amount (concentration) of the color developing agent being used in the method of the present invention is preferably in the range from 0.2 to 60 g, and more preferably from 1 to 30 g, per liter of color developer.
  • a processing temperature for a color developer is preferably in a range of 30 to 50°C, in order to achieve development in a short period of time. Also, if the developing temperature is over 50°C, Dmin (the minimum density) of color images formed is increased and hence the processing temperature is preferably lower than 50°C.
  • Color developing agents used in the method of the present invention, can be synthesized according to methods similar to those described in, e.g., the Journal of American Chemical Society, Vol. 73, 3100 (1951
  • Color developing agents used in the method of the present invention can be used alone or together with another known p-phenylenediamine derivative. Specific examples of the compounds which can be used together with the color developing agent according to the method of the present invention are illustrated below, but the present invention is not limited to these compounds.
  • these p-phenylenediamine derivatives can be used in the form of salts, such as, e.g., sulfates, hydrochlorides, sulfites, p-toluenesulfonates, nitrates, and naphthalene-1,5-disulfonates.
  • salts such as, e.g., sulfates, hydrochlorides, sulfites, p-toluenesulfonates, nitrates, and naphthalene-1,5-disulfonates.
  • An amount of aromatic primary amine developing agents can be from about 0.1 g to about 20 g per liter of color developer.
  • a p-phenylene-diamine derivative used together can be used in an amount of from 1/10 mol to 10 mols per mol of a color developing agent according to formula (I), for use in the method of the present invention.
  • the color developer comprises less than 2 ml/I benzyl alcohol, preferably less than 0.5 ml/I benzyl alcohol, and most preferably a color developer with no benzyl alcohol is used.
  • a color developer for use in the present invention also does not substantially comprise sulfite Sulfite have a function as preservatives for a color developing agent, and at the same time, function to dissolve silver halides and also to reduce dye-forming efficiency by reacting with an oxidized product of a color developing agent.
  • a function is considered to be one of the causes of increased variation in the photographic developing characteristics, associated with continuous processing.
  • does not substantially comprise sulfite ions means that the concentration of sulfite ions in a color developer, used in the present invention, is preferably less than about 3.0 X 10- 3 mol/I, and most preferably a color developer used in the present invention comprises no sulfite ions.
  • a small amount of sulfite ions, used for preventing oxidation of a developer kit, which is comprised of a concentrated color developer, diluted at use is outside the aforesaid definition in the present invention.
  • a color developer for use in the present invention does not substantially contain sulfite ions, as described above, and it is more preferred that the color developer does not substantially contain hydroxylamine.
  • hydroxylamine used as a preservative for color developers and, at the same time, has a silver development activity by itself, thereby, it is considered that the deviation of the concentration of hydroxylamine in the developer gives adverse effects on the photographic characteristics of color images formed.
  • does not substantially comprise hydroxylamine means that the concentration of hydroxylamine in the color developer is preferably less than about 5.0 X 10- 3 mol/I, and the color developer comprises most preferably no hydroxylamine.
  • a color developer for use in the present invention contains more preferably an organic preservative in place of the aforesaid hydroxylamine and sulfite ion.
  • organic preservative means all organic compounds capable of reducing the rate of deterioration of an aromatic primary amine color developing agent, by adding a color developer for color photographic light-sensitive materials, such as organic compounds having a function of preventing a color developing agent from being oxidized by air, or other compounds.
  • Examples of particularly effective organic preservatives include hydroxylamine derivatives (excluding hydroxylamine, the same applies hereinafter), hydroxamic acids, hydrazines, hydrazides, phenols, a-hydroxyketones, a-aminoketones, saccharides, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, and condensed ring type amines.
  • hydroxylamine derivatives excluding hydroxylamine, the same applies hereinafter
  • hydroxamic acids hydrazines, hydrazides, phenols, a-hydroxyketones, a-aminoketones
  • saccharides monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, and condensed ring type amines.
  • JP-A-63-4235 JP-A-63-5341, JP-A-63-30845, JP-A-63-21647, JP-A-63-44655, JP-A-63-46454, JP-A-63-53551, JP-A-63-43140, JP-A-63-56654, JP-A-63-58346, JP-A-63-43138, JP-A-63-146041, JP-A-63-44657, JP-A-63-44646, and JP-A-52-143020, U.S.
  • Patents 3,615,503 and 2,494,903, JP-B-48-30496 (the term "JP-B” as used herein refers to an "examined Japanese patent publication"), and Japanese Patent Applications 185578/89, 198676/89, and 199646/89.
  • a color developer for use in the present invention can further contain other preservatives, such as, e.g., various kinds of metals, described in JP-A-57-44148 and JP-A-57-53749; salicylic acids, described in JP-A-59-180588; alkanolamines, described in JP-A-54-3532; polyethyleneimines, described in JP-A-56-94349; and aromatic polyhydroxy compounds, described in U.S. Patent 3,746,544.
  • alkanolamines such as triethanolamine, dialkylhydroxylamines such as diethylhydroxylamine, hydrazine derivatives and aromatic polyhydroxy compounds are particularly preferred.
  • hydroxylamine derivatives and hydrazine derivatives are most preferred and details thereof are described, e.g., in JP-A-1-97953, JP-A-1-186939, JP-A-1-186940, and JP-A-1-187557.
  • Such amines include, e.g., cyclic amines, described in JP-A-63-239447, amines, described in JP-A-63-128340, and other amines, described in JP-A-1-186939 and JP-A-1-187557.
  • a color developer comprises chloride ions in an amount in the range of from about 3.5 X 10- 3 to 3.0 X 10- 1 mol/I , and more particularly from about 1 X 10- 2 to 2.0 X 10- 1 mol/I.
  • the content of chloride ions is more than about 3.0 X 10 -1 mol/I , the development is delayed and hence such a chloride content is undesirable for attaining an object of the present invention of giving high maximum density by fast processing. Also, if the chloride content is less than about 3.5 X 10- 3 mol/l, the formation of fog is increased in the developed material.
  • a color developer can be used that also comprises bromide ions in an amount of preferably from about 0.5 X 10- 5 to 1.0 ⁇ 10- 3 mol/I, and more preferably from about 3.0 X 10- 5 to 5 X 10- 4 mol/I.
  • the bromide ion concentration is more than about 1 X 10- 3 mol/I , the development is delayed and the maximum density and sensitivity are lowered, while if the bromide content is less than about 0.5 X 10- 5 mol/I, the formation of fog cannot be sufficiently prevented.
  • chloride ions and bromide ions can be directly added to a color developer or can be dissolved in a developer from color photographic light-sensitive materials during processing.
  • sodium chloride, potassium chloride, ammonium chloride, lithium chloride, nickel chloride, magnesium chloride, manganese chloride, calcium chloride, and cadmium chloride can be used as a chloride ion supplying material and sodium chloride and potassium chloride are preferred.
  • chloride ions can be supplied into a color developer from an optical whitening agent contained in a color developer.
  • bromide ion supplying material sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, magnesium bromide, manganese bromide, cerium bromide, and thallium bromide can be used and potassium bromide and sodium bromide are preferred.
  • chloride ions and bromide ions When chloride ions and bromide ions are dissolved into a developer from color photographic tight-sensitive materials, the chloride ions and the bromide ions can be supplied from silver halide emulsion layers thereof or from other layers than the emulsion layers.
  • the pH of a color developer for use in the present invention is preferably from 9 to 12, and more preferably from 9 to 11.0.
  • a color developer may further contain other components.
  • buffers include, e.g., carbonates, phosphates, borates, tetraborates, hydroxybenzoates, glycyl salts, N,N-dimethylglycine salts, leucine salts, norleucine salts, guanine salts, 3,4-dihydroxyphenylaranine salts, aranine salts, aminobutyrates, 2-amino-2-methyl-1,3-propanediol salts, valine salts, proline salts, trihydroxyamino-methane salts, lysine salts.
  • Carbonates, phosphates, tetraborates, and hydroxybenzoates are particularly preferred since they are excellent in solubility and buffer capacity in a high pH range of at least 9.0 and have the advantages that they do not give adverse effects (e.g., fogging) to the developed photographic material when they are added to a color developer. These buffers are also inexpensive.
  • Suitable examples of these buffers that can be used in the method of the present invention include sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium tertiary phosphate, potassium tertiary phosphate, sodium dihydrogenphosphate, potassium dihydrogenphosphate, sodium borate, potassium borate, sodium tetraborate (borax), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), and potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfo-salicylate).
  • the method of the present invention is not limited to these compounds.
  • the amount of the buffer being added to a color developer is preferably at least about 0.1 mol/I , and a range from about 0 1 to 0.4 mol/I is particularly preferred.
  • a color developer may contain various kinds of chelating agents for preventing the precipitation of calcium and magnesium in a color developer or for improving the stability of a color developer used in the present invention
  • Suitable chelating agents are nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,N',N'-tetramethylenesulfonic acid, trans-cyclohexanediamine-tetraacetic acid, 1,2-diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, ethylenediamine o-hydroxyphenylacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, and N,N'-bis(2-hydroxybenzyl)ethylenediamine-N,N'-diacetic acid.
  • these chelating agents can be used in combination.
  • the amount of the chelating agent can be sufficient for blocking metal ions in a color developer and can be present, for example, in concentrations from about 0.1 to 10 g per liter of color developer.
  • a color developer may further comprise a development accelerator.
  • examples include thioether series compounds, e.g., as described in JP-B-37-16088, JP-B-37-5987, JP-B-38-7826, JP-B-44-12380 and JP-B-45-9019, and U.S. Patent 3,813,247; p-phenylenediamine series compounds described in JP-A-52-49829 and JP-A-50-15554; quaternary ammonium salts described in JP-A-50-137726, JP-B-44-30074, JP-A-56-156826 and JP-A-52-43429; amine series compounds described in U.S.
  • a color developer can also comprise an optional antifoggant.
  • suitable examples are alkali metal halides such as sodium chloride, potassium bromide, potassium iodide, and organic antifoggants.
  • organic antifoggants are nitrogen-containing heterocyclic compounds such as benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chlorobenzotriazole, 2-thiazolebenzimidazole, 2-thiazolylmethylbenzimidazole, indazole, hydroxyazaindolizine and, adenine
  • a color developer for use in the present invention can comprise an optical whitening agent, such as, preferably, 4,4'-diamino-2,2'-disulfostilbene series compounds.
  • the amount of the optical whitening agent that can be used in the present invention is from about 0 to 5 g/I , and preferably from about 0.1 to 4 g/I.
  • a color developer can further comprise various kinds of surface active agents, such as alkylsulfonic acids, arylsulfonic acids, aliphatic carboxylic acids, and aromatic carboxylic acids.
  • the contact area of a photographic processing solution in a processing tank and air can be shown by the ratio defined below.
  • the aforesaid open ratio is preferably not higher than about 0.1 and preferably from about 0.001 to 0.05.
  • a method for reducing the open ratio e.g., placing a cover such as a float lid or other cover on the surface of a processing solution in a processing tank can be used, or, alternatively, using a movable lid, such as is described in JP-A-62-241342, or a slit processing process described in JP-A-63-216050.
  • a means for reducing the open ratio is applied to not only a color developer and a black-and-white developer but also to other various subsequent processing steps, such as bleaching, fixing (or bleach-fixing), washing, stabilizing.
  • a desilvering step which can be applied to the process of the present invention is further described below
  • a desilvering step is generally composed of a bleaching step and fixing step; a fixing step and a bleach-fixing (blixing) step; a bleaching step and a blixing step; or a blixing step.
  • any bleaching agents can be used but, in particular, organic complex salts (e.g., complex salts of aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, or organic phosphonic acids, such as aminopolyphosphonic acid, phosphonocarboxylic acid) of iron(III); organic acids such as citric acid, tartaric acid and malic acid; persulfates; and hydrogen peroxide are preferred.
  • organic complex salts e.g., complex salts of aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, or organic phosphonic acids, such as aminopolyphosphonic acid, phosphonocarboxylic acid) of iron(III)
  • organic acids such as citric acid, tartaric acid and malic acid
  • persulfates e.
  • organic complex salts of iron(III) are particularly preferred for fast processing and for the prevention of environmental pollution.
  • aminopolycarboxylic acid aminopolyphosphonic acid
  • organic phosphonic acid or the salts thereof useful for forming the organic complex salts of iron(III) are ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, iminodiacetic acid, and glycol ether diaminetetraacetic acid.
  • These compounds can be in the form of sodium salts, potassium salts, lithium salts or ammonium salts.
  • iron(III) complex salts of ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid, and methyliminodiacetic acid are preferred because of their high bleaching strength.
  • complex salts of ferric ions can be used in the form of a complex salt or complex salts of ferric ions can be formed in a solution by using a ferric salt (such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, or ferric phosphate), and a chelating agent (such as aminopolycarboxylic acid, aminopolyphosphoric acid, or phosphonocarboxylic acid).
  • a ferric salt such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, or ferric phosphate
  • a chelating agent such as aminopolycarboxylic acid, aminopolyphosphoric acid, or phosphonocarboxylic acid.
  • ferric complex salts a ferric salt of an aminopolycarboxylic acid is preferred and the amount thereof is from about 0.01 to 1.0 mol/l, and preferably from about 0.05 to 0.50 molll.
  • a blixing solution and/or a prebath therefor various compounds can be used as a bleach accelerator.
  • bleach accelerators are 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. 17129 (July, 1978); thiourea series compounds described in JP-B-45-8506, JP-A-52-20832 and JP-A-53-32735, and U.S. Patent 3,706,561; halides such as iodides and bromides. They are preferred due to their excellent bleaching strength.
  • a bleaching solution or a blixing solution which can be applied in the present invention can further comprise a rehalogenating agent such as a bromide (e.g., potassium bromide, sodium bromide, and ammonium bromide), a chloride (e.g., potassium chloride, sodium chloride, and ammonium chloride), and an iodide (e.g., ammonium iodide).
  • a bromide e.g., potassium bromide, sodium bromide, and ammonium bromide
  • a chloride e.g., potassium chloride, sodium chloride, and ammonium chloride
  • an iodide e.g., ammonium iodide
  • a bleaching solution or a blixing solution can comprise a corrosion inhibitor such as an inorganic acid or organic acid having a pH buffer capacity and the alkali metal or ammonium salts thereof (e.g., borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, and ammonium nitrate), and guanidine.
  • a corrosion inhibitor such as an inorganic acid or organic acid having a pH buffer capacity and the alkali metal or ammonium salts thereof (e.g., borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, and ammonium nitrate), and guanidine.
  • a corrosion inhibitor such as an inorganic acid or organic acid having a pH buffer
  • thiosulfates such as sodium thiosulfate, ammonium thiosulfate
  • thiocyanates such as sodium thiocyanate, ammonium thiocyanate
  • thioether compounds such as ethylenebisthioglycolic acid, 3,6-dithia-1,8-octanediol
  • water-soluble silver halide solvents such as thioureas
  • a specific blixing solution comprising a fixing agent and a large amount of a halide such as potassium iodide, e.g., as described in JP-A-55-155354 can be used in the present invention.
  • a halide such as potassium iodide
  • the use of thiosulfates, in particular, ammonium thiosulfate, as a fixing agent is preferred.
  • the amount of a fixing agent is preferably from about 0.3 to 2 mols, and more preferably from about 0.5 to 1.0 mol per liter of a blixing solution or a fixing solution.
  • the pH range of a blixing solution or a fixing solution is preferably from about 3 to 10, and particularly preferably from about 5 to 9.
  • a blixing solution can further contain an optical whitening agent, a defoaming agent, a surface active agent, or an organic solvent, such as polyvinylpyrrolidone, methanol.
  • a blixing solution or a fixing solution preferably contains a preservative and as a preservative, sulfite ion-releasing compounds such as sulfites (e.g., sodium sulfite, potassium sulfite, and ammonium sulfite), bisulfites (e.g., ammonium bisulfite, sodium bisulfite, and potassium bisulfite), metabi-sulfites (e.g., potassium metabisulfite, sodium metabisulfite, and ammonium metabisulfite) can be used.
  • sulfite ion-releasing compounds such as sulfites (e.g., sodium sulfite, potassium sulfite, and ammonium sulfite), bisulfites (e.g., ammonium bisulfite, sodium bisulfite, and potassium bisulfite), metabi-sulfites (e.g., potassium metabisulfite, sodium metabisulfit
  • Such a preservative is contained in the processing solution in an amount of from about 0.02 to 0.05 mol/I , and more preferably from about 0.04 to 0.40 mol/I calculated as sulfite ion.
  • sulfites are generally used but ascorbic acid, a carbonyl-bisulfite addition product, or a carbonyl compound can be also added.
  • a blixing solution or a fixing solution can further comprise a buffer, an optical whitening agent, a chelating agent, a defoaming agent or an antifungal agent.
  • a washing step and/or a stabilizing step is generally applied.
  • the amount of washing water in a washing step can be selected from a wide range of conditions according to the characteristics of the previous step (e.g., materials such as couplers used) and ultimate use of a color photographic light-sensitive materials being processed, the temperature of a washing water, the number (stage number) of washing tanks, the replenishing system (countercurrent system or normal current system), and other various circumstances.
  • the relation of a washing tanks and the amount of washing water in a multistage countercurrent system can be determined by a method, such as is described in Journal of the Society of Motion Picture and Television Enqineers, Vol. 64, 248-253 (May, 1955).
  • the stage number in a multistage countercurrent system used in the method of the present invention is preferably from about 2 to 6, and more preferably from about 2 to 4.
  • the amount of washing water can be greatly reduced to, for example, from about 0.5 to 1 liter per square meter of the color photographic material (photographic paper) with a beneficial effect of the present invention.
  • the amount of washing water there occurs a problem that by increasing the residence time in the tanks, bacteria increase and suspended matters thus formed attach to the color photographic materials being processed.
  • a method of reducing calcium and magnesium e.g., as described in JP-A-62-288838, can be very effectively used.
  • chlorine series antibacterial agents such as isothiazolone compounds and thiabendazoles described, e.g., in JP-A-57-8542 and chlorinated sodium isocyanurate described, e.g., in JP-A-61-120145; benzotriazole described, e.g., in JP-A-61-267761; copper ions; and antibacterial agents described, e.g., in Hiroshi Horiguchi, Bohkin Bohbai no Kaqaku (Antibacterial and Antifunqal Chemistry), published by Sankyo Shuppan K.K.
  • a surface active agent for use as a wetting agent, and a chelating agent such as ethylenediaminetetraacetic acid (EDTA), for use as a water softener can be used in the washing water in the method of the present invention.
  • EDTA ethylenediaminetetraacetic acid
  • a stabilizing solution comprises a compound having an image stabilizing function and examples of such a compound are aldehyde compounds such as formalin, buffers for controlling suitable pH of layers for the stabilization of dyes, and ammonium compounds.
  • a stabilizing solution can further comprise the aforesaid various kinds of antibacterial agents and antifungal agents for inhibiting the growth of bacteria in the solution and for imparting an antifungal property to the thus-developed color photographic material.
  • a stabilizing solution can also contain a surface active agent, an optical whitening agent, or a hardening agent.
  • a color photographic material can be directly processed by a stabilizing step without employing a washing step, e.g., according to methods described in JP-A-57-8543, JP-A-58-14834, and JP-A-60-220345.
  • a stabilizing solution comprises a chelating agent such as 1-hydroxyethylidene-1,1-diphosphonic acid, and ethylenediaminetetramethylenephosphonic acid, or a magnesium or bismuth compound.
  • a chelating agent such as 1-hydroxyethylidene-1,1-diphosphonic acid, and ethylenediaminetetramethylenephosphonic acid, or a magnesium or bismuth compound.
  • a so-called rinse solution can be used.
  • the pH of washing water and stabilizing solution is preferably from about 4 to 10, and more preferably from about 5 to 8.
  • the temperature for a washing step or a stabilizing step is variously selected according to the use and the characteristics of the color photographic light-sensitive material being processed, but is generally from about 15°C to about 45°C, and preferably from about 20°C to about 40°C.
  • Processing time can be variably selected but a shorter time is preferred from the viewpoint of fast processing. Processing time is preferably from about 15 seconds to about 1 minute and 45 seconds, and preferably from about 30 seconds to about 90 seconds.
  • the amount of replenisher used for a processing solution be reduced in order to lower operating cost, the amount of waste solution, and the amount of processing of waste solution.
  • the amount of replenisher used can be from about 0.5 to 50 times, and preferably from about 3 to 40 times, the amount carried by a unit area of a color photographic material from a prebath. Also, the amount thereof can be less than 1 liter, preferably less than about 500 ml per square meter of color photographic material.
  • a replenisher can be replenished continuously or intermittently.
  • Liquid used for a washing step and/or a stabilizing step can be reused for a previous step.
  • the amount of washing water is reduced by employing a multistage countercurrent system, an overflow liquid of washing water is supplied to a blixing bath which is a prebath therefor, and a concentrated liquid is replenished to the blixing bath, whereby the amount of the waste solution is reduced.
  • a color photographic material thus processed can be dried for about 10 seconds to about 10 minutes, at a temperature of from about 90°C to about room temperature.
  • a drying step may be omitted as is most suitable.
  • the aforesaid various kinds of processing solutions used in the present invention can be used at a temperature of from about 10°C to about 50°C.
  • a standard processing temperature is from about 33°C to about 38°C but it is possible to shorten the processing time by employing a higher processing temperature in order to accelerate the processing or to improve the image quality of color images formed.
  • the stability of the processing solutions is improved by employing a lower processing temperature.
  • a processing method using cobalt intensification or hydrogen peroxide intensification e.g., as described in West German Patent 2,226,770 and U.S Patent 3,674,499, can be employed.
  • the color photographic light-sensitive material (e.g., color photographic papers) being processed in the present invention generally has, on a support, at least one blue-sensitive silver halide emulsion layer, at least one green-sensitive silver halide emulsion layer, and at least one red-sensitive silver halide emulsion layer.
  • the color-sensitive silver halide emulsion layers are formed on a support in the aforesaid order but the order of the emulsion layers may differ from the aforesaid order.
  • an infrared-sensitive silver halide emulsion layer can be used in place of at least one emulsion layer described above.
  • These light-sensitive emulsion layers each comprises each silver halide emulsion having a sensitivity to each wavelength region and each so-called color coupler forming each dye in a complementary color relation with the exposing light (color), that is, yellow dye to blue, magenta dye to green, or cyan dye to red, thereby a color reproduction by subtractive color process can be performed.
  • color exposing light
  • different combinations than above, with regard to the coloring hue of each light-sensitive emulsion layer and each coupler can be employed.
  • a silver halide emulsion for use in the present invention a silver halide emulsion composed of silver chlorobromide or silver chloride and containing less than 1 mol% silver iodide can be used.
  • the content of silver iodide is preferably less than 0.2 mol%.
  • the halogen composition of the silver halide emulsion may differ among silver halide grains but, by using a silver halide emulsion having the same halogen composition among silver halide grains, the property of each silver halide grain can be easily made uniform.
  • halogen composition distribution in the inside of silver halide grains of a silver halide emulsion used in the method of the present invention can comprise (1) silver halide grains of a so-called homogeneous type structure (the halogen compositions of any portions of the silver halide grains are the same), (2) a so-called laminate layer type structure (the halogen composition of the core in the inside of the silver halide grain differs from the halogen composition of the shell (one or plural layers) surrounding the core), or (3) a structure having a non-layer form portion having a different halogen composition than that of other portion in or at the surface of the silver halide grain (when such a portion is at the surface of the silver halide grains, the grain has a structure that the portion having the different halogen composition is junctioned to the edges, corners, or the surface of the grain).
  • the latter two types of the silver halide grains are more advantageous than the former homogeneous type silver halide grains and also the latter types are also preferred for their pressure resistance.
  • the boundary portion between the portions each having a different halogen composition may form a distinct boundary or may form an indistinct boundary, formed by mixed crystals of different halogen compositions or may form a structure having a continuously changing halogen composition.
  • the halogen composition of these silver chlorobromide emulsions may have an alternative silver bromide/ silver chloride ratio. This ratio can be selected in a wide range according to the intended use of the silver halide emulsion, but a silver chlorobromide emulsion having a silver bromide content of at least about 2% can be preferably used.
  • the color photographic light-sensitive material suitable for fast processing comprises a so-called high silver chloride emulsion having a high silver chloride content
  • the silver chloride content of such a high silver chloride emulsion is at least 80 mol%, and can preferably be at least 90 mol%, and more preferably at least 95 mol%.
  • a high silver chloride emulsion has preferably the aforesaid structure wherein local silver bromide-containing portions exist in the interior and/or at the surface of silver halide grains, as a layer form or a non-layer form.
  • the silver bromide content is preferably at least about 10 mol%, and more preferably over about 20 mol%.
  • these local silver bromide-containing portions can exist in the interior of the silver halide grains or at the edges, corners, or other surfaces of the grains.
  • silver halide grains of a heterogeneous type structure having a narrow distribution of halogen composition in the grains for a high silver chloride emulsion e.g., having a silver chloride content of at least 90 mol%.
  • an almost pure silver chloride emulsion having the silver chloride content of from about 98 mol% to 100 mol% is also preferably used.
  • Mean grain size (the number mean value of the diameters of circles equivalent to the projected areas of grains as the grain sizes) of the silver halide grains contained in the silver halide emulsion for use in the present invention is preferably from about 0.1 to 2 pm.
  • the grain size distribution of silver halide grains is preferably a so-called monodispersed distribution having a coefficient of variation (i.e., the standard deviation of the grain size distribution divided by the mean grain size) of about 20% or less, and preferably about 15% or less. I n this case, it is preferred to use the aforesaid monodispersed emulsion in the same emulsion layer as a blend thereof or in double layers for obtaining a wide tolerance.
  • Silver halide grains contained in a silver halide photographic emulsion for use in the present invention may have a regular crystal form such as cubic, tetradecahedral, or octahedral, an irregular crystal form such as spherical or tabular, or a composite form of these crystal forms.
  • a silver halide emulsion contains silver halide grains having the aforesaid regular crystal form in an amount of at least about 50%, preferably at least about 70%, and more particularly at least about 90%.
  • a silver halide emulsion containing silver halide grains wherein tabular silver halide grains having an aspect ratio (circle-calculated length/thickness) of at least about 5, and preferably at least about 8, which accounts for at least 50% of the total projected area of the silver halide grains, can be preferably used.
  • Silver chlorobromide emulsion for use in the present invention can be prepared according to the methods described, e.g., in P. Glafkides, Chimie et Physique Photoqraphique, published by Paul Montel, 1967; G.F. Duffin, Photographic Emulsion Chemistry, published by Focal Press, 1966; and VL. Zelikman et al., Makinq and Coating Photographic Emulsion, published by Focal Press, 1964.
  • a silver halide emulsion can be prepared by an acid method, a neutralization method, or an ammonia method, and, as a system of reacting a soluble silver salt and a soluble halide, a single jet method, a double jet method, or a combination thereof can be employed.
  • a so-called reverse mixing method of forming silver halide grains in the existence of excess silver ions can also be employed.
  • a so-called controlled double jet method of keeping a constant pAg in a liquid phase for forming silver halide grains can also be used. According to such a method, a silver halide emulsion comprising silver halide grains having a regular crystal size and substantially uniform grain sizes can be obtained.
  • a silver halide emulsion for use in the present invention, can be introduced various kinds of multivalent metal ion impurities in a step of forming the silver halide grains or a step of physical ripening of the emulsions.
  • metal ion impurities are salts of cadmium, zinc, lead, copper or thallium; and salts of complex salts of elements belonging to Group VIII of the Periodic system, such as iron, ruthenium, rhodium, palladium, osmium, iridium or platinum.
  • the aforesaid elements belonging to the Group VIII can be preferably used.
  • the amount of these compounds can be selected in a wide range according to the purpose of their use but is preferably from about 10- 9 to 10- 2 mol per mol of silver halide.
  • Silver halide emulsions for use in the present invention are usually subjected to chemical sensitization and to optical sensitization.
  • a sulfur sensitization such as the addition of an unstable sulfur compound, a noble metal sensitization such as a gold sensitization, or a reduction sensitization can be applied singly or as a combination thereof.
  • Preferred compounds which are used for chemical sensitization are described in JP-A-62-215272, pages 18 to 22.
  • Optical sensitization is applied for imparting an optical sensitivity to a desired wavelength region of each silver halide emulsion layer of the color photographic light-sensitive material being processed in the present invention.
  • a spectral sensitizing dye i.e., a dye that absorbs light of a wavelength region corresponding to the desired spectral sensitization.
  • spectral sensitizing dyes being used in the present invention are described in F.M. Hamer, Heterocyclic Compounds, Cyanine Dyes and Related Compounds, published by John Wiley & Sons (New York, London, 1964).
  • a silver halide emulsions for use in the present invention may be a so-called surface latent image type emulsion which mainly forms latent images on the surfaces of silver halide grains or a so-called internal latent image type emulsion which mainly forms latent images in the interior of the grains.
  • a yellow coupler, a magenta coupler, and a cyan coupler forming yellow, magenta, and cyan, respectively, can be coupled with the oxidation product of an aromatic amino color developing agent.
  • Cyan couplers, magenta couplers, and yellow couplers which can be preferably used in the present invention are shown by the following formulae (C-I) or (C-II), (M-I) or (M-II), and (Y), respectively.
  • magenta couplers having an amino-releasing group at a coupling position or pyrazoloazole based magenta couplers are preferably used.
  • Magenta couplers of formula (M-I), in which Y 3 is a releasable group, or of formula (M-II) are more preferred and magenta couplers of formula (M-II) are particularly preferred.
  • R 1 , R 2 , and R 4 each represents a substituted or unsubstituted aliphatic group, a substituted or unsubstituted aromatic group, or a substituted or unsubstituted heterocyclic group;
  • R 3 , R 5 , and R 6 each represents a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group, or an acylamino group, said R 3 may form a nonmetallic atomic group forming a nitrogen-containing 5-membered or 6-membered ring together with R 2 ;
  • Y 1 and Y 2 each represents a hydrogen atom or a group capable of releasing at the coupling reaction with the oxidation product of an aromatic primary amino color developing agent; and
  • n represents 0 or 1.
  • R 5 is preferablyan aliphatic group and examples thereof are methyl, ethyl, propyl, butyl, pentadecyl, tert-butyl, cyclohexyl, cyclohexylmethyl, phenylthiomethyl, dodecyloxyphenylthiomethyl, butanamidomethyl, and methoxyethyl.
  • R 1 is preferably an aryl group ora heterocyclic group and is more preferably an aryl group substituted by a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an acylamino group, an acyl group, a carbamoyl group, a sulfonamido group, a sulfamoyl group, a sulfonyl group, a sulfamido group, an oxycarbonyl group or a cyano group
  • R 2 is preferably a substituted or unsubstituted alkyl group or aryl group, and particularly preferably an alkyl group substituted by a substituted aryloxy group; and R 3 is preferably a hydrogen atom.
  • R 4 is preferably a substituted or unsubstituted alkyl group or aryl group, and particularly preferred is an alkyl group substituted by a substituted aryloxy group.
  • R 5 is preferably an alkyl group having from 2 to 15 carbon atoms or a methyl group having a substituent of at least one carbon atom and examples of the substituent are an arylthio group, an alkylthio group, an acylamino group, an aryloxy group, and an alkyloxy group.
  • R 5 is more preferably an alkyl group having from 2 to 15 carbon atoms and is particularly preferably an alkyl group having from 2 to 4 carbon atoms.
  • R 6 is preferably a hydrogen atom or a halogen atom, and particularly preferably chlorine or bromine.
  • Y 1 and Y 2 are preferably a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, or a sulfonamido group.
  • R 7 and Rg each represents an aryl group which may be substituted;
  • R 8 represents a hydrogen atom, an aliphatic or aromatic acyl group, or an aliphatic or aromatic sulfonyl group; and
  • Y 3 represents a hydrogen atom or a releasable group.
  • the aryl group (preferably a phenyl group) shown by R 7 and Rg may be substituted as described above and examples of the substituent are those described above on the aryl group shown by R 1 in formula (C-I) and when the aryl group has two or more substituents, they may be the same or different.
  • R 8 is preferably a hydrogen atom, an aliphatic acyl group or an aliphatic sulfonyl group, and particularly preferably a hydrogen atom.
  • Y 3 which is preferred for stabilization of color images obtained by a fast development process using compounds of the above described formula (I) is a releasing group of a type of releasing by a sulfur, oxygen or nitrogen atom and is particularly preferably a sulfur atom-releasing type group as described in U.S. Patent 4,351,897 and WO 88/04795.
  • R 10 represents a hydrogen atom or a substituent and Y 4 represents a hydrogen atom or a releasing group, and particularly preferably a halogen atom or an arylthio group.
  • the Z b -Z c bond is a carbon-carbon double bond, it is a part of an aromatic ring.
  • the coupler shown by formula (M-II) can include formation of a dimer or a polymer at R 10 or Y 4 or when Z a , Z b or Z c is a substituted methine group, it includes formation of a dimer or a polymer at the substituted methine.
  • imidazo[1,2-b]pyrazoles described in US. Patent 4,500,630 are preferred when there is less yellow side adsorption and light fastness of colored dyes and the pyrazolo [1,5-b][1,2,4]triazoles described in U.S. Patent 4,540,654 are particularly preferred.
  • pyrazolotriazole couplers having a branched alkyl group directly bonded to the 2-, 3-or 6-position of the pyrazolotriazole ring e.g., as described in JP-A-61-65245
  • pyrazoloazole couplers having a sulfonamido group in the molecule as described e.g., in JP-A-61-65246
  • pyrazoloazole couplers having an alkoxyphenylsulfonamido ballast group as described e.g., in JP-A-61-147254
  • pyrazolotriazole couplers having an alkoxy group or an aryloxy group at the 6-position as described e.g., in European Patent Publications 226,849 and 294,785 are preferably used.
  • R 11 represents a halogen atom, an alkoxy group, a trifluoromethyl group, or an aryl group
  • R 12 represents a hydrogen atom, a halogen atom, or an alkoxy group
  • A represents -NHCOR 13 , -NHS0 2 -R 13 , -SO 2 NHR 13 , -COOR 13 , or (wherein R 13 and R 14 each represents an alkyl group, an aryl group or an acyl groups
  • Y 5 represents a releasable group
  • the groups shown by R 12 , R 13 , and R 14 may have a substituent and examples of the substituent are those shown above on R 1 in formula (C-I).
  • the releasable group shown by Y 5 is a group released by an oxygen atom or a nitrogen atom, and further a nitrogen atom-releasable type is particularly preferred.
  • Couplers shown by formulae (C-I), (C-II), (M-I), (M-II), and (Y) described above are illustrated below.
  • each of the couplers shown by the aforesaid formulae (C-I) to (Y) is incorporated in a silver halide emulsion layer constituting the color photographic light-sensitive material from 0.1 to 1.0 mol, and preferably from 0.1 to 0.5 mol, per mol of the silver halide in the emulsion.
  • an oil drop-in-water dispersion method which is also known as an oil protect method, can be employed. That is, after dissolving the coupler in an organic solvent, the solution is dispersed by emulsification in an aqueous gelatin solution containing a surface active agent. Alternatively, water or an aqueous gelatin solution is added to a coupler solution in an organic solvent containing a surface active agent to form an oil-in-water dispersion with phase inversion.
  • the coupler when the coupler is soluble in an alkaline aqueous solution, the coupler can be dispersed by a so-called Fischer's dispersion method.
  • the dispersion After removing a low boiling organic solvent from a coupler dispersion by distillation, noodle washing, or ultrafiltration, the dispersion may be mixed with a photographic emulsion.
  • a high boiling organic solvent having a dielectric constant of from about 2 to 20 (25°C) and a refractive index of from about 1.5 to 1.7 (25°C) and/or a water-insoluble high molecular compound is preferably used.
  • the high boiling organic solvents shown by, but not limited to, the following formulae (A) to (E) are preferably used.
  • W i , W 2 and W 3 each represents an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, or a heterocyclic group, each group may be substituted or unsubstituted;
  • W 4 represents W 1 , OW 1 , or S-W 1 ; and
  • n represents an integer of from 1 to 5, when n is 2 or more, W 4 s may be the same or different, and also W 1 and W 2 in formula (E) may form a condensed ring.
  • a melting point of a high boiling organic solvent which can be used in the method of the present invention is preferably not higher than about 80°C and the boiling point thereof is preferably at least about 160°C, and more preferably at least about 170°C.
  • Typical examples of such high boiling organic solvents are described, e.g., in JP-A-62-215272, pages 137, right lower column to 144, right upper column.
  • the aforesaid coupler can be emulsion-dispersed in an aqueous solution of a hydrophilic colloid by impregnating a loadable latex polymer with a coupler in the presence or absence of the aforesaid high boiling organic solvent (e.g., U.S. Patent 4,203,716) or by dissolving the coupler in a water-insoluble and organic solvent-soluble polymer or homopolymer.
  • aforesaid high boiling organic solvent e.g., U.S. Patent 4,203,716
  • Such a homopolymer or polymer e.g., acrylamide series polymers described in WO 88/00723, are preferably used for stabilizing color images in the method of the present invention.
  • a color photographic light-sensitive material processed by the process of the present invention can comprise, e.g., hydroquinone derivatives, aminophenol derivatives, gallic acid derivatives, and ascorbic acid derivatives, as color fog inhibitors.
  • various fading inhibitors can also be used.
  • organic fading inhibitors for cyan, magenta, and/or yellow color images there are hindered phenols such as hydroquinones, 6-hydroxychromans, 5-hydroxycoumarans, spirochromans, p-alkoxyphenols, and bisphenols; gallic acid derivatives; methylenedioxybenzenes; aminophenols; hindered amines; and the ether or ester derivatives formed by silylating or alkylating the phenol hydroxy group of each of the aforesaid compounds.
  • metal complexes such as (bissalicylaldoximato)nickel complexes and (bis-N,N-dialkyldithiocarbam- ato)nickel complexes can be used.
  • organic fading inhibitor examples include, e.g., hydroquinones described in U.S. Patents 2,360,290, 2,418,613, 2,700,453, 2,701,197, 2,728,659, 2,732,300, 2,735,765, 3,982,944, 4,430,425, 2,710,801 and 2,816,028, and British Patent 1,363,921; 6-hydroxychromans, 5-hydroxycoumarans, and spirochromans described in U.S. Patents 3,432,300, 3,573,050, 3,574,627, 3,698,909 and 3,764,337, and JP-A-52-152225; spiroindanes described in U.S.
  • Patent 4,360,589 p-alkoxyphenols described in U.S. Patent 2,735,765, British Patent 2,066,975, JP-A-59-10539 and JP-B-57-19765; hindered phenols described in U.S. Patents 3,700,455 and 4,228,235, JP-A-52-72224 and JP-B-52-6623; gallic acid derivatives, methylenedioxybenzenes, and aminophenols described in U.S. Patents 3,457,079 and 4,332,886 and JP-B-56-21144; hindered amines described in U.S.
  • Patents 3,336,135 and 4,268,593 British Patents 1,326,889, 1,354,313 and 1,410,846, JP-B-51-1420, JP-A-58-114036, JP-A-59-53846 and JP-A-59-78344; and metal complexes described in U.S. Patents 4,050,938 and 4,241,155 and British Patent 2,027,731 (A).
  • An organic fading inhibitor as described above, can be coemulsified with a corresponding color coupler in an amount of from about 5 to 100% by weight, and then added to a light-sensitive silver halide emulsion layer, and used in the method of the present invention.
  • an ultraviolet absorber can be introduced into a cyan coloring emulsion layer and layers adjacent to both sides of the cyan coloring layer, as used in the method of the present invention.
  • ultraviolet absorbers examples include benzotriazole compounds substituted by an aryl group described, e.g., in U.S. Patent 3.,533,794; 4-thiazolidone compounds described, e.g., in U.S. Patents 3,314,794 and 3,352,681; benzophenone compounds described, e.g., in JP-A-46-2784; cinnamic acid ester compounds described, e.g., in U.S. Patents 3,705,805 and 3,707,395; butadiene compounds described, e.g., in U.S. Patent 4,045,229; and benzoxazole compounds described, e.g., in U.S. Patents 3,406,070, 3,677,672 and 4,271,307.
  • ultraviolet absorptive couplers e.g., a-naphthol series cyan dye forming couplers
  • ultraviolet absorptive polymers can be mordanted to specific emulsion layers.
  • benzotriazole compounds substituted by an aryl group described above are preferred.
  • coupler it is preferred to use the aforesaid coupler together with each of the following compounds.
  • coupler pyrazoloazole couplers are particularly preferred.
  • a coupler is used together with a compound (F) (as described herein) forming a chemically inert and substantially colorless compound by chemically bonding with an aromatic amino color developing agent remaining after color development and/or a compound (G) (as described herein) forming a chemically inert and substantially colorless compound by chemically bonding with an oxidation product of an aromatic amino color developing agent remaining after color development since the formation of stains and the occurrence of other undesirable side reactions by the reaction of the coupler and the color developing agent or the oxidation product thereof, remaining in the photographic emulsion layers of color photographic materials during the storage thereof after processing, can be prevented.
  • a compound (F) as described herein
  • G as described herein
  • a compound (F) is capable of reacting with p-anisidine at a secondary reaction rate constant k 2 (in trioctyl phosphate at about 80°C) in the range of from about 1.0 f/mol.s to 1 X 10- 5 f/mol.s.
  • the secondary reaction rate constant k 2 described above can be measured by a method described, e.g., in JP-A-63-158545.
  • k 2 is larger than the aforesaid range, the compound itself becomes unstable and sometimes decomposes by reacting with gelatin or water
  • k 2 is less than the aforesaid range, the reaction with the remaining aromatic amino developing agent is delayed, which results in the inhibition of side reactions by the remaining aromatic amino color developing agent.
  • a compound (F) is more preferably a compound represented by the following formula (FI) or (FII): wherein R 1 and R 2 each represents an aliphatic group, an aromatic group, or a heterocyclic group; n represents 0 or 1; A represents a group forming a chemical bond by reacting with an aromatic amino developing agent; X represents a group released by reacting with an aromatic amino color developing agent; B represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, or a sulfonyl group; and Y represents a group of accelerating the addition of an aromatic amino color developing agent to the compound of formula (FII); said R 1 and X, or said Y and R 2 or B may combine with each other to form a ring structure.
  • R 1 and R 2 each represents an aliphatic group, an aromatic group, or a heterocyclic group
  • n 0 or 1
  • A represents a group forming a chemical bond by reacting with
  • Typical systems for chemically bonding the aforesaid compound and the remaining aromatic amino color developing agent are a displacement reaction and an addition reaction.
  • Z is a group wherein the Pearson's nucleophilic n CH 3 1 value (R.G. Pearson et al., Journal of American Chemical Society, 90, 319 (1968)) is at least 5 or a group derived from that group.
  • a color photographic light-sensitive material being processed by the method of the present invention may contain a water-soluble dye or a dye which becomes water-soluble by photographic processing in a hydrophilic colloid layer, as a filter dye, or for preventing irradiation and halation, and for other various purposes.
  • a water-soluble dye or a dye which becomes water-soluble by photographic processing in a hydrophilic colloid layer as a filter dye, or for preventing irradiation and halation, and for other various purposes.
  • Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes, and azo dyes. In these dyes, oxonol dyes, hemioxonol dyes, and merocyanine dyes are preferred.
  • gelatin is advantageously used but other hydrophilic colloid can be also used solely or together with gelatin.
  • gelatin being used may be lime-processed gelatin or acid-processed gelatin. Details of the production of such a gelatin are described, e.g., in Arther Vaise, The Macromolecular Chemistry of Gelatin, published by Academic Press, 1964.
  • a transparent film such as a cellulose nitrate film or a polyethylene terephthalate film (which is usually used for photographic films) or a reflection type support can be used
  • a reflective support is more preferably used.
  • reflective support means a support clearly showing the color images formed in the silver halide emulsion layer(s) formed thereon by increasing the reflectivity of the support.
  • a reflective support includes a support coated with a hydrophobic resin containing, dispersed therein, a light reflecting material, such as titanium oxide, zinc oxide, calcium carbonate, and calcium sulfate, and a support composed of a hydrophobic resin containing the aforesaid light reflecting material.
  • Examples of a reflective support are baryta-coated papers, polyethylene-coated papers, polypropylene synthetic papers, and transparent supports such as glass sheets, films of polyesters (such as polyethylene terephthalate, cellulose triacetate and cellulose diacetate), polyamide films, polycarbonate films, polystyrene films, vinyl chloride series films which can be coated or mixed with the aforesaid reflective material.
  • transparent supports such as glass sheets, films of polyesters (such as polyethylene terephthalate, cellulose triacetate and cellulose diacetate), polyamide films, polycarbonate films, polystyrene films, vinyl chloride series films which can be coated or mixed with the aforesaid reflective material.
  • a support having a mirror plane reflective or second kind of reflective metal surface can be used.
  • a metal surface has preferably a spectral reflectivity in a visible wavelength range of at least 0.5 and also is preferred to render the metal surface diffuse-reflective by roughening the surface or using a metal powder.
  • the surface of the support may be the surface of a metal plate formed by rolling or a metal thin layer formed by vapor deposition or plating. Also, the surface may be formed by a metal foil. Of these supports, a support having a vapor-deposited metal layer is preferably used
  • a layer of a water resisting resin be formed, in particular, a thermoplastic resin.
  • an antistatic layer is formed on the opposite side of the support to the metal surface side. Details of these supports are described in JP-A-61 -210346, JP-A-63-24247, JP-A-63-24251 and JP-A-63-24255. These supports are selected according to which purpose they are used for.
  • a white pigment in the presence of a surface active agent, and also pigment particles, the surfaces of which have been treated with di- to tetrahydric alcohol are preferably used.
  • the occupied area ratio (%) per defined unit area of white pigment fine particles can be most typically determined by dividing an observed area into adjacent area of about 6 pm X 6 ⁇ m each and measuring the occupied area ratio (%) (R ; ) of the fine particles projected to each unit area.
  • the coefficient of variation of the occupied area ratio (%) can be determined by the ratio (s/R) of the standard deviation (s) of R, to the mean value (R) of R.
  • the number (n) of the unit areas being measured is preferably 6 or more.
  • the coefficient of variation s/R can be obtained by the following equation:
  • the coefficient of variation of the occupied area ratio (%) of the fine particles of a pigment is preferably less than about 0.15, and particularly preferably less than about 0.12.
  • the coefficient of variation is less than about 0.08, the dispersibility of the particles can be said to be substantially "uniform"
  • a fast process for color prints which are usually used, is used but the present invention can be applied to an intelligent color hard copy requiring fast processing.
  • a scanning light exposure using a high density light such as laser (e.g., semiconductor laser) or a light emitting diode can be preferably employed.
  • Semiconductor lasers usually have a high light sensitivity in the infrared region and hence a color photographic light-sensitive material being used for such a system can have at least one infrared light-sensitive silver halide emulsion layer in place of the aforesaid silver halide emulsion layer(s), when used in the method of the present invention.
  • each silver halide emulsion has a sensitivity in each wavelength region and each of so-called color couplers forming each dye of a complementary color to each sensitizing light (i.e., yellow to blue, magenta to green, and cyan to red)
  • a color reproduction by a subtractive color process can be practiced.
  • the light-sensitive emulsion layers and the coloring hues of color couplers may employ other constituents than those described above.
  • two kinds of color couplers may be used and in this case, the number of silver halide emulsion layers corresponding to these couplers may be two. In this case, full color images are not obtained but color images can be formed faster.
  • color photographic light-sensitive materials can be processed in a shorter period of time and also processed more stably in continuous processing than conventional methods.
  • the present invention can provide a method for processing silver halide color photographic materials capable of giving both high storage stability of formed color images and the fast processing property. Also, in the present invention, a processing system giving less waste solutions with low replenisher processing is possible. Moreover, the use of 5-pyrazolone magenta couplers having an anion-releasing group at a coupling position or pyrazoloazole based magenta couplers as magenta couplers can be used to obtain color images having a high storage stability and, in particular, an excellent light fastness.
  • Coating compositions for the layers were prepared as follows.
  • a blue-sensitive sensitizing dye described below was added to a silver chlorobromide emulsion (cubic form, mean grain size: 0.88 pm, variation coefficient of the grain size distribution: 0.08, the silver halide grain had locally on the surface thereof 0.2 mol% silver bromide) in an amount of 2.0 X 10- 4 mol per mol of silver
  • a blue-sensitive sensitizing dye described below was also added to a silver chlorobromide emulsion (cubic form, mean grain size: 0.70 pm, variation coefficient of grain size distribution: 0.10, the silver halide grain had locally on the surface thereof 0.2 mol% silver bromide) in an amount of 2.5 X 10- 4 mol per mol of silver
  • the former emulsion was mixed with the latter emulsion at a ratio of 3/7 (by mol ratio of silver)
  • a sulfur sensitization was applied to the mixed emulsion.
  • the aforesaid emulsified dispersion was mixed with the mixed emulsion
  • Coating compositions for the second layer to the seventh layer were prepared in a manner similar to the above.
  • each dye was added as 2.0 X 10- 4 mol for the silver halide emulsion of large grain size and 2.5 X 10- 4 mol for the silver halide emulsion of small grain size per mol of silver halide)
  • the blue-sensitive emulsion layer was added 1-(5-methylureidophenyl)-5-mercaptotetrazole in the amounts of 8.5 X 10- 5 mol, 7.7 X 10- 4 mol, and 2.5 X 10- 4 mol, respectively, per mol of silver halide.
  • each emulsion layer was added the following dyes for irradiation prevention.
  • compositions of the layers are shown below.
  • the numerals shown below are coating amounts (g/m 2 ), wherein the case of each silver halide emulsion is shown by the coated amount calculated as silver.
  • Polyethylene Coated Paper (the polyethylene layer at the emulsion side on the support contained a white pigment (TiO 2 ) and a bluish dye (ultramarine blue))
  • Second Layer Color Mixing Inhibiting Layer
  • the compounds used for the color photographic paper were as follows.
  • UV-1) UV Absorber (UV-1) UV Absorber:
  • the sample thus prepared was subjected to a gradation exposure through a sensitometric trichromatic separation filter using an actinometer (color temperature of light source: 3,200°K).
  • the exposure was carried out such that the exposure amount became 250 CMS in an exposure time of 0.1 second.
  • the sample thus exposed was processed by the following processing steps using the processing solutions having the compositions shown below.
  • compositions of the processing solutions were as follows.
  • Blixinq Solution composition of the tank liquid was the same as that of the replenisher
  • the minimum density (Dmin) and the maximum density (Dmax) were measured through each of blue (B), green (G), and red (R) filters corresponding to the dyes.
  • color photographic materials were prepared in the same manner as for the above described color photographic materials but changing the halogen composition in the silver halide emulsions used in the emulsion layers to those set forth below.
  • Silver chlorobromide emulsion (1/3 mixture (mol ratio of Ag) of cubic silver chlorobromide containing 80.0 mol% of AgBr and having mean grain size of 0.85 ⁇ m and variation coefficient of 0.08 and cubic silver chlorobromide containing 80.0 mol% AgBr and having mean grain size of 0.62 pm and variation coefficient of 0.07)
  • Silver chlorobromide emulsion (1/1 mixture (mol ratio of Ag) of cubic silver chlqrobromide containing 90 mol% of AgBr and having mean grain size of 0.47 ⁇ m and variation coefficient of 0 12 and cubic silver chlorobromide containing 90 mol% AgBr and having mean grain size of 0.36 ⁇ m and variation coefficient of 0.09)
  • Silver chlorobromide emulsion 1/2 mixture (mol ratio of Ag) of cubic silver chlorobromide containing 70 mol% of AgBr and having mean grain size of 0.49 ⁇ m and variation coefficient of 0.08 and cubic silver chlorobromide containing 70 mol% AgBr and having mean grain size of 0.34 ⁇ m and variation coefficient of 0.10)
  • the samples thus obtained were exposed to a xenon lamp (300,000 lx) for 8 days, and thereafter the reduction of the image densities after the light irradiation was measured. (Shown by the density after light irradiation of the images at the exposure amount portion of giving FD:image density of 1.0. FD: density after light fading.)
  • a color photographic paper having the same layer structures as in Example 1 was prepared and processed by the following processing steps.
  • the sample was subjected to a gradation exposure through a sensitometric trichromatic separation filter using an actinometer (color temperature of light source: 3,200°K).
  • the exposure was carried out such that the exposure amount for an exposure time of 0.1 second was 250 CMS
  • compositions of the processing solutions were as follows.
  • Blixinq Solution the composition of tank liquid was the same as that of the replenisher
  • Rinsing Solution the composition of tank liquid was the same as that of the replenisher
  • the density of each of the yellow, magenta, and cyan color images was measured through each of a blue, green, and red filters corresponding to each dye and the minimum density (Dmin), the maximum density (Dmax), and the relative sensitivity (S: a relative value when the sensitivity of Sample 2 at 30 seconds was defined to be 100) were calculated.
  • the sample obtained by processing of the development time of 30 seconds was exposed to a xenon lamp (300,000 lx) and thereafter the reduction of the image density by the light irradiation was measured (shown by the density after the light irradiation of the images at the exposure amount portion of giving FD:image density of 1.0.
  • FD Density after light fading
  • color images having high Dmax and a high light fastness are obtained even in processing of a short time, such as 30 seconds or less.
  • Example 2 The same procedure as in Example 2 was followed except that the color developing agent in the color developer was changed as shown in Table 3 below and the developing time was changed to 20 seconds.
  • an aqueous solution containing 0.780 mol of silver nitrate and an aqueous solution containing 0.780 mol of sodium chloride and 4.2 mg of potassium ferrocyanide were added to the mixture with stirring vigorously at 56°C.
  • an aqueous solution containing 0.020 mol of silver nitrate and an aqueous solution containing 0.015 mol of potassium bromide, 0.005 mol of sodium chloride, and 0.8 mg of potassium hexachloroiridate (IV) were added to the mixture with stirring vigorously at 40°C.
  • the form of the silver halide grains, the grain sizes, and the grain size distribution thereof were determined from the electron microphotographs thereof.
  • the mean grain size was shown by the mean value of the diameters of circles equivalent to the projected areas of the grains and the variation coefficient of the grain size distribution was shown by the value obtained by dividing the standard deviation of the grain sizes by the mean grain size.
  • the halogen composition of the silver halide grains was determined.
  • the monochromatic CuKa line as the X-ray source, the diffraction angles from the (200) plane were measured in detail.
  • the diffraction line from the silver halide crystals having a uniform halogen composition gave a simple peak, while the diffraction line from the silver halide crystals having a local phase having a different halogen composition gave plural peaks corresponding to these compositions.
  • the lattice constant from the measured diffraction angles of the peaks, the halogen composition of silver halide constituting the silver halide crystals was determined.
  • a multilayer color photographic paper having the layers shown below on a paper support having polyethylene coating on both sides.
  • the coating compositions for the layers were prepared as follows.
  • a mixed solvent of 27.2 ml of ethyl acetate and 8.2 g of a solvent (Solv-1, as shown herein) were dissolved 19.1 g of a yellow coupler (ExY) and 4.4 g of a color image stabilizer (Cpd-1), and the solution obtained was emulsified and dispersed in 185 ml of an aqueous 10% gelatin solution containing 8 ml of an aqueous 10% solution of sodium dodecylbenzenesulfonate.
  • a silver halide emulsion was prepared by adding a red-sensitive sensitizing dye (Dye-1) to the aforesaid silver chlorobromide emulsion (A). The aforesaid emulsified dispersion was mixed with the silver halide emulsion and the composition of the mixture was adjusted as shown belowto provide a coating composition for the first layer.
  • the coating compositions for the second layer to the seventh layer were also prepared by the similar manner to the above.
  • 1-oxy-3,5-dichloro-s-triazine sodium salt was used as a gelatin hardening agent for each layer.
  • the following dyes were used as spectral sensitizing dyes for each layer.
  • each of the yellow coloring emulsion layer, the magenta coloring emulsion layer, and the cyan coloring emulsion layer was added 1-(5-methylureido-phenyl)-5-mercaptotetrazole in an amount of 8.0 X 10- 4 mol per mol of silver halide.
  • compositions of the layers are shown below.
  • the numerals are coating amounts (g/m 2 ), wherein the case of silver halide emulsion is shown by the coating amount calculated as silver.
  • Polyethylene Coated Paper (the polyethylene layer at the emulsion layer side on the support contained a white pigment (Ti0 2 ) and a bluish dye (ultramarine blue))
  • Second Layer Color Mixing Inhibiting Layer
  • a scanning exposure apparatus capable of exposing a color photographic paper by successively scanning by a semiconductor laser AIGaInP (oscillation wavelength: about 670 nm), a semiconductor laser GaAlAs (oscillation wavelength: about 750 nm), and a semiconductor laser GaAlAs (oscillation wavelength: about 810 nm) such that the laser light struck the color photographic paper traveling in the direction perpendicular to the scanning direction of the laser lights from a rotary polyhedron was prepared, and the color photographic papers were exposed using this apparatus.
  • the exposure amounts were controlled by electrically controlling the exposure time and the light emitting amount of the semiconductor lasers.
  • compositions of the processing solutions used are as set forth below.
  • Blixina Solution (The composition of the replenisher was the same as that of the tank liquid.)
  • Rinsing Solution (The composition of the replenisher was the same as that of the tank liquid.)
  • the rinsing (3) liquid was sent under pressure using a plastic pressure resisting vessel apparatus Type PV-0321, trade name, equipped with an inverse osmosis membrane (polysulfone series composite film, effective film area: 1.1 m 2 ) under the conditions of a liquid sending pressure of 4 kg/cm 2 and a flow rate of 1.5 l/min.
  • the liquid thus osmosed was supplied to the rinsing tank (4) and the concentrated liquid was returned to the rinsing tank (3).
  • Color photographic papers were prepared in the same manner as in Example 4 but replacing magenta coupler ExM in the third layer (magenta-coloring layer) in Example 4 by an equimolar amount of the compounds indicated in Table 5. As color developing agents the compounds indicated in Table 5 were used. The color photographic papers thus prepared were processed and evaluated in the same manner as in Example 4.
  • Couplers M-4 and ExM provide better light fastness, with the latter being still better than the former.
  • Couplers M-4 and ExM are used for obtaining better results in the prevention of the stain formation, with the latter coupler being still better than the former one.
  • Color photographic papers were prepared in the same manner as in Example 5 but replacing the magenta coupler in the third layer (magenta-coloring layer) in Example 4 by an equimolar amount of the compounds indicated in Table 6.
  • the color photographic materials so prepared were processed and evaluated in just the same manner as in Example 5. The results are shown in Table 6.

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  • Physics & Mathematics (AREA)
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Claims (13)

1. Procédé pour développer un matériau photographique couleur à l'halogénure d'argent exposé suivant une image qui comprend le développement d'un matériau photographique couleur contenant des grains d'halogénure d'argent dans une émulsion d'halogénure d'argent, ladite émulsion comprenant () moins de 1 mole % d'iodure d'argent et (ii) au moins 80 moles % de chlorure d'argent, avec un révélateur comprenant (i) moins de 2 ml/1 d'alcool benzylique et (ii) un dérivé de p-phénylènediamine représenté par la formule (1):
Figure imgb0162
dans laquelle R1 et R3 représentent chacun un groupe alkyle en C1-C4 et R2 représente un groupe alkylène à chaîne droite ou ramifiée en C3 ou C4 et dans lequel ledit développement est effectué en une durée de 30 s ou moins.
2. Procédé selon la revendication 1, dans lequel R2 représente un groupe alkylène à chaîne droite ou ramifiée en C4.
3. Procédé selon la revendication 1, dans lequel ladite durée est de 20 s ou moins.
4. Procédé selon la revendication 1, dans lequel ladite couche d'émulsion d'halogénure d'argent comprend au moins 90 moles % de chlorure d'argent
5. Procédé selon la revendication 1, dans lequel ladite couche d'émulsion d'halogénure d'argent comprend au moins 95 moles % de chlorure d'argent
6. Procédé selon la revendication 1, dans lequel ledit dérivé de p-phénylènediamine est présent à une concentration dans l'intervalle de 0,2 à 60 g/1 de révélateur.
7. Procédé selon la revendication 1, dans lequel ledit dérivé de p-phénylènediamine est présent à une concentration dans l'intervalle de 1 à 30 g/I de révélateur.
8. Procédé selon la revendication 1, dans lequel ledit alcool benzylique est présent à une concentration de moins de 0,5 ml/1 de révélateur.
9. Procédé selon la revendication 1, dans lequel ledit développement est effectué à une température d'au moins 30°C.
10. Procédé selon la revendication 1, dans lequel ledit développement est effectué à une température dans l'intervalle de 30 à 50°C.
11. Procédé selon la revendication 1, dans lequel ledit développement est effectué à un pH dans l'intervalle de 9 à 12.
12. Procédé selon la revendication 1, dans lequel ledit développement est effectué à un pH dans l'intervalle de 9 à 11.
13. Procédé selon la revendication 1, dans lequel ledit matériau photographique couleur a une couche d'halogénure d'argent sensible au vert contenant un coupleur pour magenta du type 5-pyrazolone ayant un groupe libérant un anion introduit dans une position de couplage ou un coupleur pour magenta du type pyrazoloazole.
EP19900114363 1989-07-28 1990-07-26 Procédé de traitement de matériaux photographiques couleur à l'halogénure d'argent Expired - Lifetime EP0410450B1 (fr)

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JPH05107706A (ja) * 1991-08-19 1993-04-30 Fuji Photo Film Co Ltd ハロゲン化銀カラー写真感光材料及びその処理方法
JP2847273B2 (ja) * 1991-11-22 1999-01-13 富士写真フイルム株式会社 カラー画像形成方法
JPH05216191A (ja) * 1992-02-05 1993-08-27 Fuji Photo Film Co Ltd ハロゲン化銀カラー写真感光材料の処理方法
JP2840895B2 (ja) * 1992-02-18 1998-12-24 富士写真フイルム株式会社 カラー画像形成方法
EP0585679A1 (fr) * 1992-09-01 1994-03-09 Konica Corporation procédé de formation d'une image photographique couleur
JPH06167789A (ja) * 1992-11-30 1994-06-14 Fuji Photo Film Co Ltd カラー画像形成方法
JPH06175304A (ja) * 1992-12-04 1994-06-24 Konica Corp ハロゲン化銀カラー感光材料及びカラー画像形成方法
US5443943A (en) * 1993-03-22 1995-08-22 Eastman Kodak Company Method of processing originating photographic elements containing tabular silver chloride grains bounded by {100} faces
DE69424983T2 (de) 1993-11-24 2000-10-19 Fuji Photo Film Co., Ltd. Photographische Verarbeitungszusammensetzung und Verarbeitungsverfahren
JP2000356844A (ja) 1999-06-16 2000-12-26 Fuji Photo Film Co Ltd ハロゲン化銀カラー写真感光材料及びその現像処理方法
EP1886784A1 (fr) * 2006-08-09 2008-02-13 Pfizer Products Inc. Procédé et dispositif de serrage

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JPS5916261B2 (ja) * 1978-12-20 1984-04-14 富士写真フイルム株式会社 カラ−画像形成方法
AU590563B2 (en) * 1985-05-16 1989-11-09 Konishiroku Photo Industry Co., Ltd. Method for color-developing a silver halide color photographic light-sensitive material
JPS6311938A (ja) * 1986-03-26 1988-01-19 Konica Corp ハロゲン化銀カラ−写真感光材料の処理方法
JPH0750327B2 (ja) * 1986-06-06 1995-05-31 富士写真フイルム株式会社 カラ−画像形成方法及びハロゲン化銀カラ−写真感光材料
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