EP0279464A2 - Verfahren zur Behandlung von farbphotographischen Silberhalogenidmaterialien und farbphotographische Entwicklungszusammensetzung - Google Patents

Verfahren zur Behandlung von farbphotographischen Silberhalogenidmaterialien und farbphotographische Entwicklungszusammensetzung Download PDF

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Publication number
EP0279464A2
EP0279464A2 EP88102484A EP88102484A EP0279464A2 EP 0279464 A2 EP0279464 A2 EP 0279464A2 EP 88102484 A EP88102484 A EP 88102484A EP 88102484 A EP88102484 A EP 88102484A EP 0279464 A2 EP0279464 A2 EP 0279464A2
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Prior art keywords
group
processing
formula
color developing
composition
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EP88102484A
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English (en)
French (fr)
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EP0279464A3 (en
Inventor
Takatoshi C/O Fuji Photo Film Co. Ltd. Ishikawa
Nobutaka C/O Fuji Photo Film Co. Ltd. Ohki
Morio C/O Fuji Photo Film Co. Ltd. Yagihara
Hiroshi C/O Fuji Photo Film Co. Ltd. Fujimoto
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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Priority claimed from JP62037351A external-priority patent/JPS63204258A/ja
Priority claimed from JP11594787A external-priority patent/JPH01105247A/ja
Application filed by Fuji Photo Film Co Ltd filed Critical Fuji Photo Film Co Ltd
Publication of EP0279464A2 publication Critical patent/EP0279464A2/de
Publication of EP0279464A3 publication Critical patent/EP0279464A3/en
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/407—Development processes or agents therefor
    • G03C7/413—Developers

Definitions

  • the present invention relates to a method for processing a silver halide color photographic material and a color photographic developing composition used in the method, and more particularly to a method for processing a silver halide color photographic material in which the stability and the color-forming property of a color photographic developing solution are improved, and the increased fogging problem in continuous processing is lessened; and a color developing composition which can afford the color developing solution.
  • Color developing solutions containing an aromatic primary amine color developing agent have long been used or forming color images, and they now play a main role in methods of forming color photographic images.
  • these color developing solutions have the disadvantage of oxidizing easily with air or metals, and if color images are formed using oxidized color developing solution there is increased fogging or the sensitivity or gradation changes, thus interfering with the desired photographic properties.
  • sulfite ions have long been used to improve the preservative property of various developing agents or to prevent hydroxyl amines from decomposing, they greatly hamper the color-forming property and markedly lower the color density. Especially when the sulfite ion is used in a system free of benzyl alcohol which is desirable to avoid the solution-preparation and environmental pollution problems involved with benzyl alcohol.
  • preservatives can be mentioned aromatic polyhydroxy compounds described, for example, in Japanese Patent Application (OPI) Nos. 49828/1977, 160142/1984, and 47038/1981 and U.S.Patent No.3,746,544, hydroxycarbonyl compounds described in U.S. Patent No. 3,615,503 and British Patent No. 1,306,176, a-aminocarbonyl compounds described in Japanese Patent Application (OPI Nos. 143020/1977 and 89425/1978, metal salts described in Japanese Patent Application (OPI) Nos.
  • chelating agents can be mentioned amino polycarboxylic acids described in Japanese Patent Publication Nos. 30496/1973 and 30232/1969; organic phosphonic acids described in Japanese Patent Application (OPI) No. 97347/1981, Japanese Patent Publication No. 39359/1981, and West German Patent No. 2,227,639; phosphonocarboxylic acids described, for example, in Japanese Patent Application (OPI) Nos. 102726i1977, 42730/1978, 121127/1979, 126241/1980, and 65956/1980; compounds described, for example, in Japanese Patent Application (OPI) Nos. 195845/1983 and 2003440/1983 and Japanese Patent Publication No. 40900/1978; and organic phosphonic acid type chelating agents described in Research Disclosure Nos. 18837 and 17048.
  • an object of the invention is to provide a method of processing a silver halide color photographic material wherein the stability of the color developing solution is excellent and the increase in fogging during continuous processing is very low.
  • a further object of the invention is to provide a method of processing a silver halide color photographic material that is excellent in color-forming property regardless of the fact that it is processed with a color developing solution substantially free from benzyl alcohol.
  • Still a further object of the invention is to provide a color developing solution excellent in stability, color-forming property and the prevention of solution-preparation and environmental poiution problems.
  • a method of processing a silver halide color photographic material in which the silver halide color photographic material is processed with a color developing solution containing an aromatic primary amine color developing agent, at least one organic phosphonic acid type chelating agent and at least one compound represented by formula (I) given below.
  • X represents a trivalent group of atoms required to complete a condensed ring
  • R, and R 2' which may be the same or different, each represent an alkylene group, an arylene group, an alkenylene group, or an aralkylene group.
  • a color developing composition for processing a silver halide color photographic material which comprises an aromatic primary amine color developing agent, at least one organic phosphonic acid type chelating agent and a compound represented by the above formula (I).
  • the color developing composition may be used as a color developing solution, as it is, or after adjusting its composition.
  • Japanese Patent Application (OPI) No. 265149/1986 has described that compounds represented by formula (I) improve the stability of color developing solutions.
  • the present invention is distinguished from the application in that the compound is used with an organic phosphonic acid chelating agent and the effect of the present invention is remarkable.
  • the number of carbon atoms of X is preferably 20 or below, more preferably 10 or below, and even more preferably 6 or below.
  • X may include atoms of, for example, nitrogen, oxygen, and sulfur.
  • the number of carbon atoms of R, and R 2 is preferably 10 or below, more preferably 6 or below, and even more preferably 3 or below.
  • R, and R 2 are an alkylene group or an arylene group, more preferably an alkylene group.
  • the compounds represented by formula (1) may be in a bis-form or a tris-form connected through X.
  • R, and R z of formula (I) methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a 1,2-cyclohexylene group, a 1-methylethylene group, a 1,2-dimethylethylene group, a 1-carboxyethylene group, a 1,2-phenylene group, a 1,2-vinylene group, and a 1,3-propenylene group, which may be substituted, for example, by an alkyl group, a halogen atom, a carboxyl group, a sulfo group, a hydroxyl group, an alkoxy group, an alkylthio group, an amino group, an amide group, an acyl group, a carbamoyl group, a sulfamoyl group, or a heterocyclic ring group.
  • R 3 has the same meaning as R, or R 2 or represents In formula (I-a), preferably X represents .
  • the number of carbon atoms of R,, R 2 , and R 3 is 6 or below, more preferably 3 or below, and most preferably 2.
  • R, R 2 , and R 3 represent an alkylene group or an arylene group, most preferably an alkylene group.
  • R, and R2 have the same meaning as defined in formula (I).
  • R, and R2 represent an alkylene group or an arylene group, most preferably an alkylene group.
  • the amount of the compounds of formula (I) to be added is preferably 0.1 g to 50 g, more preferably 0.2 to 20 g, per liter of a color developing solution.
  • organic phosphonic acids used in the invention may be any of organic phosphonic acids such as alkylphosphonic acids, phosphonocarboxylic acids and amonopolyphosphonic acids. They are given by the following formulae:
  • A, to A 6 each represents a substituted or unsubstituted alkylene group;
  • Z represents an alkylene group, a cyclohexane group, a phenylene group, -R-O-R-, -ROROR-,
  • R represents an alkylene group and A 7 represents a hydrogen atom a hydrocarbon, a lower aliphatic carboxylic acid or a lower alcohol; and B, D, E. F and G each represent -OH, -COOM, or -PO 3 M 2 in which M represents a hydrogen atom, an alkali metal, or ammonium, provided that at least one of B, C, D, E, F, and G is -PO 3 M 2 .
  • Examples of the color developing solution used in the present invention may include a conventional aromatic primary amine color developing agent.
  • Preferred examples of aromatic primary amine color developing agents are p-phenylenediamine derivatives. Representative examples are given below, but they are not meant to limit the present invention:
  • p-phenylenediamine derivatives may be in the form of salts such as sulfates, hydrochlorides, sulfites, and p-toluenesulfonates.
  • the amount of the aromatic primary amine developing agent to be used is preferably about 0.1 g to about 20 g, more preferably about 0-5 g to about 10 g, per liter of developing solution.
  • the present color developing solution be substantially free of benzyl alcohol.
  • substantially free of benzyl alcohol means that the amount of benzyl alcohol per liter of color developing solution is no more than 2 m c, but more preferably benzyl alcohol should not be contained at all.
  • a sulfite such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite, and potassium metasulfite, or a carbonyl sulfite adduct may be added to the color developing solution.
  • the preservative may be added in an amount of 0 g to 20 g, preferably 0 g to 5 g, per liter of developing solution. A smaller amount is preferable, provided that the stability of the color developing solution is retained.
  • a compound to preserve directly the above-mentioned developing agent such as hydroxylamines, hydroxamic acids described in Japanese Patent Application No 186559/1986, hydrazines and hydrazides described in Japanese Patent Application No. 170756/1986, phenols described in Japanese Patent Application Nos. 188742/1986 and 203253/1986, 0-hydroxyketones and a-aminoketones described in Japanese Patent Application No. 188741/1986, and/or succharides described in Japanese Patent Application No. 180616/1986, in combination with a compound represented by formula (I).
  • hydroxylamines such as hydroxylamines, hydroxamic acids described in Japanese Patent Application No 186559/1986, hydrazines and hydrazides described in Japanese Patent Application No. 170756/1986, phenols described in Japanese Patent Application Nos. 188742/1986 and 203253/1986, 0-hydroxyketones and a-aminoketones described in Japanese Patent Application No. 188741/1986
  • preservatives may also be contained, such as, metals described in Japanese Patent Application (OPI) Nos. 44148/1982 and 53749/1982, salicyclic acids described in Japanese Patent Application (OPI) No. 180588/1984, alkanolamines described in Japanese Patent Application (OPI) No. 3532/1979, polyethyleneimines described in Japanese Patent Application (OPI) No. 94349/1981, and aromatic polyhydroxy compounds described in U.S Patent No. 3,746,544.
  • the pH of the color developing solution of the present invention is in the range of 9 to 12, more preferably 9 to 11.0, and other known compounds that are components of a conventional developing solution can be contained.
  • Buffer agents that can be used include carbonates phosphates, borates, tetraborates, hydroxybenzoates, glycine salts, N,N-dimethylglycine salts, leucine salts, norleucine salts, guanine salts, 3,4-dihydroxyphenylalanine salts, alanine salts, aminobutyrates, 2-amino-2-methyl-1,3-propanediol salts, valine salts, proline salts, trishydrox- yaminomethane salts and lysine salts.
  • carbonates, phosphates, tetraborates, and hydroxybenzoates are excellent in solubility and buffer performance at a high pH of 9.0 or above, and when added to the color developing solution there are no adverse effects (e.g., fogging) on photographic performance. Additionally they are inexpensive, so it is particularly preferable to use these buffer agents.
  • buffer agents sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, 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-sulfosalicylate).
  • the present invention is not limited to these compounds.
  • the amount of the buffer agent to be added to the color developing solution is 0.1 mol/liter or over, more preferably 0.1 to o.4 mol/liter.
  • Various chelating agents other than organic phosphonic acid series can be used together in the color developing solution.
  • chelating agents examples include nitrilotriacetic acid, dietylentriaminepentaacetic acid, ethylenediaminetetraacetic acid, transcyclohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, ethylendiamineorthohydroxyphenylacetic acid, N,N'-bis(2-hydroxybenzyl)-ethylenediamine-N,N'-diacetic acid, and hydroxyethyliminodiacetic acid.
  • Two or more of these chelating agents may be combined if required.
  • development accelerators may be added to the color developing solution if required.
  • development accelerators that can be mentioned are thioether type compounds described in Japanese Patent Publication Nos. 16088/1962, 5987/1962, 7826/1963, 12380/1969, 9019/1970, and U.S.Patent No. 3,813,247; p-phenylenediamine compounds described in Japanese Patent Application (OPI) Nos. 49829/1977 and 15554/1975; quaternary ammonium salts described in Japanese Patent Application (OPI) No. 137726/1975, Japanese Patent Publication No. 30074/1969, Japanese Patent Application (OPI) Nos. 156826/1981 and 43429/1977; amine type compounds described in U.S. Patent Nos.
  • Antifoggants that can be added include alkali metal halides such as sodium chloride, potassium bromide, and potassium iodide, and organic antifoggants.
  • organic antifoggants include nitrogen-containing heterocyclic compounds such as benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolylbenzimidazole, 2-thiazolylmethylbenzimidazole, indazoles, hydroxyazindolizine, and adenine.
  • surface active agents such as alkyl sulfonic acids, aryl phosphonic acids, aliphatic carboxylic acids, and aromatic carboxylic acids may be added.
  • the processing temperature using the present color developing solution is between 20 to 50°C, preferably 30 to 40°C.
  • the processing time is between 20 sec. to 5 min., preferably 30 sec. to 2 min. It is preferable to use a smaller amount of reprenisher, generally 20 to 600 mt., preferably 50 to 300 mt, and more preferably 100 to 200 m per m 2 of the photographic material. The shorter the developing time the beffer for attaining the remarkable effect of the present invention.
  • organic complex salts of iron (III) e.g., complex salts of aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, aminopolyphosphonic acids, phosphonocarboxylic acids, and organic phosphonic acids
  • organic acids such as citric acid, tartaric acid, and malic acid
  • persulfates and hydrogen peroxide e.g., citric acid, tartaric acid, and malic acid.
  • organic complex salts of iron (III) are particularly preferable to achieve rapid processing and to prevent environmental contamination.
  • Aminopolycarboxylic acids, aminopolyphosphonic acids, and organic phosphonic acids or their salts useful for forming organic complex salts of iron (III) include ethylenediaminetetraacetic acid, diethylenetriaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, and glycol ether diaminetetraacetic acid. These compounds may be any one of sodium salt, potassium salt, lithium salt, and ammonium salt.
  • ethylenediaminetetraacetic acid diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid, or methyliminodiacetic acid, since their bleaching power is high.
  • ferric ion complex salts may be used in the form of a complex salt, or a ferric ion complex salt may be formed in solution using a ferric salt such as ferric sulfate, ferric chloride, ferric nitrate, ammonium iron (III) sulfate, and ferric phosphate and chelating agent such as an aminopolycarboxylic acid, an aminopolyphosphonic acid, and a phosphonocarboxylic acid.
  • a ferric salt such as ferric sulfate, ferric chloride, ferric nitrate, ammonium iron (III) sulfate, and ferric phosphate and chelating agent such as an aminopolycarboxylic acid, an aminopolyphosphonic acid, and a phosphonocarboxylic acid.
  • ferric salts such as ferric sulfate, ferric chloride, ferric nitrate, ammonium iron (III) sulfate, and ferric phosphate and chel
  • a chelating agent is used in excess to form a ferric ion complex salt.
  • iron complex salts aminopolycarboxylic acid iron complex salts are preferable, and the amount used is 0.01 to 1.0 moliliter, preferably 0.05 to 0.50 mol/liter.
  • the bleaching solution and the bleach-fixing solution and/or their preceding bath solution may have a bleach accelerating agent.
  • useful bleach accelerating agents can be mentioned compounds having a mercapto group or a disulfido group described, for example, in U.S. Patent No. 3,893,858, West German Patent No. 1,290,812, Japanese Patent Application (OPI) No. 95630/1978, and Research Disclosure No. 171129 (July 1978), thiourea derivatives described in Japanese Patent Publication No. 8506/1970, Japanese Patent Application (OPI) Nos. 20832/1977 and 32735/1978 and U.S. Patent No. 3,706,561, and halide compounds (iodide, bromide). These compounds are preferable in view of high acceleration effects.
  • the bleaching solution or the bleach-fixing solution used in the present invention may contain 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) or an iodide (e.g., ammonium iodide).
  • 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) or an iodide (e.g., ammonium iodide).
  • 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 ammoni
  • the fixing agent used in the bleach-fixing solution or the fixing solution of the present invention can be a known fixing agent. That is, a dissolving agent of water-soluble silver halide, for example a thiosulfate such as sodium thiosulfate or ammonium thiosulfate; a thiocyanate such as sodium thiocyanate or ammonium thiocyanate; a thioether compound such as ethylenebisthioglycolic acid or 3,6-dithia-1,8-octanediol; or a thiourea. Two or more of these compounds may be combined.
  • a dissolving agent of water-soluble silver halide for example a thiosulfate such as sodium thiosulfate or ammonium thiosulfate; a thiocyanate such as sodium thiocyanate or ammonium thiocyanate; a thioether compound such as ethylenebisthioglycoli
  • a special bleach-fixing solution comprising a combination of a large amount of a halide such as potassium iodide and a fixing agent described in Japanese Patent Application (OPI) No. 155354/1980 can be used.
  • a thiosulfate particularly ammonium thiosulfate.
  • the amount of a fixing agent to be used per liter of the bath is preferably in the range of 0-3 to 2 mol, more preferably 0-5 to 1.0 mol.
  • the pH range of the bleach-fixing solution or the fixing solution is preferably in the range of 3 to 10, more preferably 5 to 9.
  • the bleach-fixing solution can contain a brightening agent, an antifoamer, a surface active agent, or an organic solvent such as polyvinylpyrolidone and methanol.
  • the bleach-fixing solution or the fixing solution in the present invention contains, as a preservative, a sulfite ion releasing compound such as a sulfite (e.g., sodium sulfite potassium sulfite, and ammonium sulfite), a bisulfite (e.g , ammonium bisulfite, sodium bisulfite, and potassium bisulfite), and a metabisulfite (e.g., potassium metabisulfite, sodium metabisulfite, and ammonium metabisulfite)
  • a sulfite ion releasing compound such as a sulfite (e.g., sodium sulfite potassium sulfite, and ammonium sulfite), a bisulfite (e.g , ammonium bisulfite, sodium bisulfite, and potassium bisulfite), and a metabisulfite (e.g., potassium metabisulfite, sodium meta
  • a sulfite is generally added as a preservative, an ascorbic acid and a carbonyl-bisulfite adduct or a carbonyl compound can be added.
  • a buffering agent for example, a buffering agent, brightening agent, chelating agent, or antifungal agent.
  • a shorter processing time of the desilvering step shows a more marked effect, so the time of the desilvering step is preferably 2 min. or less, more preferably 1 min. or less.
  • the silver halide color photographic material used in the present invention is generally passed through a washing step and/or a stabilizing step after the desilvering process of fixing or bleach-fixing.
  • the amount of washing water in the washing step can be set in a wide range depending on the properties of the photographic material (for example, due to the material used, such as couplers), the uses of the photographic material, the temperature of the washing water, the number of washing tanks (number of steps), the type of replenishing mode such as counter-current mode or concurrent mode, and other conditions.
  • the relationship between the number of washing tanks and the amount of water in the multistage counter-current mode can be determined according to a method described in Journal of the Society of Motion Picture and Television Engineers, Vol. 64, pp. 248-253 ( May 1955).
  • the number of steps of the multistage counter-current washing mode is preferably 2 to 6, more preferably 2 to 4.
  • the effect of the present invention appears more remarkable.
  • the amount of washing water can be decreased considerably, below 1 liter, preferably 0-5 liter, per m 2 of photographic material.
  • bacteria propagate due to the increased time the water remains in the tanks, causing problems such as the adhesion of resulting suspended matter on the photographic material.
  • a method of decreasing calcium and magnesium described in Japanese Patent Application No. 131632/1986 can be used very effectively.
  • agents that can be used include isothiazolone and cyabendazole compounds described in Japanese Patent Application (OPI) No.
  • chlorine-type bactericides such as sodium chlorinated isocyanurate described in Japanese Patent Application (OPI) No. 120145/1986, benzotriazole described in Japanese Patent Application No. 105487/1985, copper ion and other bactericides described in Hiroshi Horiguchi Bokinbobai no Kagaku, Biseibutsu no Mekkin, Sakkin, Bobai Gijutsu, edited by Eiseigijutsu kai, and Bokinbobaizai Jiten, edited by Nihon Bokinbobai-gakkai.
  • OPI Japanese Patent Application
  • benzotriazole described in Japanese Patent Application No. 105487/1985
  • copper ion and other bactericides described in Hiroshi Horiguchi Bokinbobai no Kagaku, Biseibutsu no Mekkin, Sakkin, Bobai Gijutsu, edited by Eiseigijutsu kai, and Bokinbobaizai Jiten, edited by Nihon Bo
  • a surface active agent as a drainer and a chelating agent such as EDTA (ethylenediamine tetraacetate) as a water-softener can be used.
  • the stabilizing solution includes a compound having an image stabilizing function.
  • an aldehyde compound represented by formalin for example an aldehyde compound represented by formalin; a buffer to adjust the film pH suitable for dye- stabilization; and an ammonium compound.
  • An above-mentioned bactericide or fungicide can be also used to prevent the propagation of bacteria in the solution and to give a fungus-proof property to the photographic material.
  • a surface active agent, fluorescent brightening agent, and a film-hardner can be added.
  • all the known methods described, for example, in Japanese Patent Application (OPI) Nos. 8543/1982, 14834/1983, 184343/1984, 220345/1985, 238832/1985, 239784/1985; 239749/1985, 4054/1986, and 118749/1986 can be used.
  • a preferred inclusion is to use a chelating agent such as 1-hydroxyethylidene-1,1-diphosphonate, and a magnesium or bismuth compound.
  • the amount of stabilizing solution, as with the washing solution, can be decreased considerably (below 1 liter, more preferably below 0.5 liter) by using a multistage counter-current method.
  • the washing water or stabilizing solution may be replenished either continuously or intermittently. If intermittently, replenishing may be done depending on the processing volume or in a certain interval of time.
  • the pH range of the washing or stabilizing solution in the present invention may be 4 to 10, preferably 5 to 8.
  • the temperature which can be set according to the use or the property of the photographic material, is generally in the range of 15 to 45°C, preferably 20 to 40°C.
  • time can be set arbitrary, the effect of the present invention is remarkable with a shorter processing time, preferably 30 sec. to 2 min., more preferably 30 sec. to 1 min. 30 sec.
  • a smaller amount of replenisher is preferable in view of the running cost, the decrease in discharge volume, ease of treatment, and the effect of the present invention.
  • the volume of the replenisher is 0-5 to 50 times, preferably 3 to 40 times, the carried-over volume from the preceding bath per unit area of the photographic material.
  • Solutions used in the washing and/or stabilizing steps can be adopted in the preceding step.
  • the volume of waste solution can be reduced by introducing the over-flowed washing water cut by the multistage counter-current method into the preceding bleach-fixing bath and by replenishing a concentrated solution into the bleach-fixing bath.
  • the method of this invention can be applied to any processing process using a color developing solution.
  • it can be applied to processing color paper, color reversal paper, color direct positive photosensitive material, color positive film, color negative film, or color reversal film. It is preferable for application to the processing of color paper or color reversal paper that is sensitive to contamination of stain parts.
  • the silver halide emulsion of the color photographic material to be use in this invention may be any type of halogen composition, including silver iodobromide, silver bromide silver chlorobromide, or silver chloride.
  • a silver chlorobromide emulsion containing 80 mol% or more of silver chloride or a silver chloride emulsion is preferable, and a silver halide emulsion containing 90 to 100 mol% is especially preferable.
  • the silver halide crystals of the silver halide emulsion in this invention may be of such a structure that the internal phase differs from the surface phase, the entire crystals may have a uniform phase, they may be polyphase with a joining structure, or a mixture thereof.
  • the average size of the silver halide grains expressed in terms of the grain diameter for spherical or semi-spherical grains and the edge length for cubic grains, can be determined as the average of the projected area diameter, etc., and it is preferably smaller than 2 um and larger than 0.1 ⁇ m, most preferably smaller than 1-5 u.m and larger than 0.15 u.m.
  • the distribution of grain size may be either narrow or wide.
  • a monodisperse emulsion of silver halide may be employed in the present invention.
  • the monodisperse emulsion may have a fluctuation coefficient as a monodisperse index of 20% or less, preferably 15% or less, the coefficient of which is obtained by dividing the standard deviation calculated from the curve of the size distribution to the average particle size.
  • two or more monodisperse silver halide emulsions different in grain size may be mixed in a single layer or coated as different layers that have essentially the same color sensitivity.
  • two or more polydisperse silver halide emulsions or a - combination of monodisperse and polydisperse emulsions can be employed as a mixture in one layer, or coated as different layers.
  • Silver halide grains for use in this invention may have a regular crystal structure such as cubic, hexahedral, rohmbic dodecahedral, or tetradecanhedral, an irregular crystal structure such as spherical, or a thereof composite crystal structure.
  • Tabular grains may be employed wherein at least 50% of the total projected area of silver halide grains is tabular grains with a diameter-to-thickness ratio of about 5 to 8 particularly of about 8 or more.
  • Silver halide emulsions may be a mixture of various crystal structures.
  • Silver halide grains may be used which form a latent image primary on the grain surface or in the interior of the grains.
  • the photographic emulsion for use in this invention can be prepared by the process described in Research Disclosure (RD) Vol. 170 Item 17643 (I, II, III)(Dec. 1978).
  • the emulsion to be used in this invention may be physically ripened, chemically ripened, and spectrally sensitized. Additives that will be used in these steps are described in Research Disclosure Vol. 176, No. 17643 (Dec. 1978) and ibid. Vol. 187, No. 18716 (Nov. 1979), and the involved sections are listed in the Table below.
  • color coupler means a compound which can form dye by a coupling reaction with an oxidized aromatic primary amine developing agent.
  • Typical and useful color couplers are naphthol or phenol compounds, pyrazolone or pyrazoloazol compounds, and open chain or heterocyclic ketomethylene compounds. Examples of these cyan, magenta and yellow couplers are disclosed in patents cited in Research Disclosure (RD) No. 17643 (Dec. 1978), VII-D and ibid. No. 18717 (Nov. 1979).
  • Color couplers for incorporation in the present photographic materials are preferably nondiffusible by being ballasted or polymerized.
  • Two-equivalent couplers with a coupling-off group at the coupling-active position are more preferable than four-equivalent couplers having only hydrogen at the coupling position, in view of reduced silver coverage.
  • Couplers can be employed in the present invention which form a dye of controlled image smearing or a colorless compound, as well as DIR couplers which release a development inhibiting reagent upon a coupling reaction, and couplers releasing a development accelerating agent.
  • yellow couplers useful in this invention include couplers of the oil-protected acylacetoamide type, as illustrated in U.S. Patent Nos. 2,407,210, 2,875,057, and 3,265,506.
  • Typical examples of two-equivalent yellow couplers preferable in this invention include yellow couplers having an oxygen-linked coupling-off group as illustrated in U.S. Patent Nos. 3,408,194, 3,447,928, 3,933,501, and 4,022,620; yellow couplers having a nitrogen-linked coupling-off group as illustrated in Japanese Patent Publication No. 10739/1983.
  • Couplers of the a-pivaloyl-acetoanilide type are superior in the fastness of formed dye, particularly on exposure to light, while couplers of the a-benzoylacetoanilide type are capable of forming high maximum density.
  • Magenta couplers useful for this invention include oil-protected couplers of the indazolone or cyanoacetyl type, preferable of the 5-pyrazolone or pyrazoloazole (e.g., pyrazolotriazole) type.
  • 5-Pyrazolones substituted by an arylamino or acylamino group at the 3-position are preferable in view of the hue and maximum densities of formed dyes, and are illustrated in U.S. Patent Nos. 2,311,082, 2,343,703, 2,600,788, 2,908,573, 3,062,653, 3,152,896, and 3,936,015.
  • Preferable coupling-off groups in the two-equivalent 5-pyrazolone couplers are nitrogen-linked coupling-off groups described in U.S. Patent No. 4,310,619, and an arylthio group described in U.S. Patent No. 4,351,897.
  • the ballast groups described in European Patent No. 73,636 have effects to enhance developed density in the 5-pyrazolone couplers.
  • Preferred pyrazoloazole coupler can be represented by the following formula (Xll):
  • R 1 represents a hydrogen atom or substituent
  • X represents a hydrogen atom or a group which can be split-off upon coupling reaction with the oxidation product of an aromatic primary amine as a developing agent
  • the coupler may be a dimer or polymer connected through R 1 or X.
  • Za, Zb, or Zc is a substituted methine, it may also be a dimer or polymer connected through the substituted methine.
  • polymer used in connection with the compound represented by formula (XII) means those compounds which have in one molecule two or more moiety, represented by formula (XII). Such compounds include dimer and polymer couplers.
  • the polymer coupler may be a homopolymer composed solely of a monomer component having the moiety represented by formula (XII) (preferably monomers having a vinyl group referred to as vinyl monomer hereinafter).
  • the polymer coupler may also be a copolymer containing a non-color-forming ethylenic monomer which does not undergo coupling with the oxidation product of an aromatic primary amine.
  • the compounds represented by formula (XII) are couplers having 5-membered ring-5-membered ring condensed nitrogen-containing heterocyclic ring.
  • Their color-forming mother nuclear has an aromatic property equal to naphthalene in electron and has a chemical structure ordinarily called "azapentalene”.
  • Preferred coupler-compounds represented by formula (XII) include 1H-imidazo [1,2-b]-pyrazoles, 1 H-pyrazolo[1,5-b]pyrazoles, 1 H-pyrazolo[5,1-c][1,2,4]triazoles, 1 H-pyrazolo[1,5-b][1,2,4]triazoles, 1 H-pyrazolo [1,5-d]tetrazoles and 1H-pyrazolo[1,5-a]benzimidazoles which are represented by the following formulae (XIII), (XIV), (XV), (XVI), (XVII) and (XVIII), respectively. Of those, especially preferred compounds are those represented by formulae (XIII), (XV) and (XVI), in which further preferred compounds are those represented by formula (XVI).
  • the substituted groups R 11 , R 12 and R 13 independently represent a hydrogen atom, halogen atom, alkyl group, aryl group, heterocyclic group, cyano group, alkoxyl group, aryloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, silyloxy group, sulfonyloxy group, acylamino group, anilino group, ureido group, imido group, sulfamoylamino group, carbamoylamino group, alkylthio group, arylthio group, heterocyclic thio group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamido group, carbamoyl group, acyl group, sulfamoyl group, sulfonyl group, sulfinyl group, alkoxycarbonyl group
  • the coupler may be a polymer coupler in which the coupler residue represented by formulae (XIII) to (XVIII) is on the principal chain or side chain of the polymer.
  • the polymer is derived from a vinyl monomer having the moiety represented by formulae (XII) to (XVIII)
  • R", R 12 , R 13 , or X represents a mere bond or a connecting group through which moieties represented by formulae (XII) to (XVIII) bond to the vinyl moiety.
  • R 11 , R 12 and R 13 each represent a hydrogen atom, halogen atom (e.g., chlorine atom, and bromine atom), alkyl group (e.g., methyl, propyl, iropropyl, t-butyl, trifluoromethyl, tridecyl, 2-[a- ⁇ 3-(2-octyloxy-5-tert-octylbenzenesulfonamido)phenoxy ⁇ tetradecanamido]ethyl, 3-(2,4-di-t-amylphenoxy)-propyl, allyl, 2-dodecyloxyethyl, 1-(2-octyloxy-5-tert-octylbenzenesulfonamido)-2-propyl, 1-ethyl-1- ⁇ 4-(2-butoxy-5-tert-octylbenzenesulfonamido)phenyl ⁇ methyl, 3-phen
  • X represents a hydrogen atom, halogen atom (e.g., chlorine atom, bromine atom, and iodine atom), carboxyl group, group connected through an oxygen atom (e.g., acetoxy, propanoyloxy, benzoyloxy, 2,4-dichlorobenzoyl, ethoxyoxaloyloxy, pyruvinyloxy, cinnamoyloxy, phenoxy, 4-cyanophenoxy, 4-methanesul- fonamidophenoxy, 4-methanesulfonylphenoxy, a-naphthoxy, 3-pentadecylphenoxy, benzyloxycarbonyloxy, ethoxy, 2-cyanoethoxy, benzyloxy, 2-phenethyloxy, 2-phenoxyethoxy, 5-phenyltetrazolyloxy, and 2-ben- zothiazolyloxy), group connected through a nitrogen atom (e
  • R" R 12 , R 13 , or X is a divalent group to form a dimer
  • R", R 12 , and R' 3 independently represent a substituted or unsubstituted alkylene group (e.g., methylene, ethylene, 1,10- decylene, and -CH 2 CH 2 -O-CH 2 CH 2 -), substituted or unsubstituted phenylene group e.g., 1,4-phenylene, 1,3-phenylene, , -NHCO-R 14 group (wherein R 14 represents a substituted or unsubstituted alkylene group or phenylene group).
  • a substituted or unsubstituted alkylene group e.g., methylene, ethylene, 1,10- decylene, and -CH 2 CH 2 -O-CH 2 CH 2 -
  • substituted or unsubstituted phenylene group e.g., 1,4-phenylene, 1,3-pheny
  • examples of the connecting group represented R 11 , R 12 , R 13 , and X include those groups selected from substituted or unsubstituted groups (e.g., methylene, ethylene, 1,10-decylene, and -CH 2 CH 2 -O-CH 2 CH 2 -), substituted or unsubstituted phenylene groups (e.g., 1,4-phenylene, 1, 3-phenylene, ), -NHCO-, CONH-, -0-, -OCO-, and aralkylene group (e.g., and combination thereof.
  • substituted or unsubstituted groups e.g., methylene, ethylene, 1,10-decylene, and -CH 2 CH 2 -O-CH 2 CH 2 -
  • substituted or unsubstituted phenylene groups e.g., 1,4-phenylene, 1, 3-phenylene,
  • -NHCO- CONH-, -0-, -OCO-, and
  • the vinyl group may have a substituent group other than the group represented by formulae (XIII) to (XVIII).
  • the preferred substituent group is a hydrogen atom, chlorine atom, or lower alkyl group having 1 to 4 carbon atoms (e.g., methyl and ethyl).
  • the monomer containing the group represented by formulae (XIII) to (XVIII) may form a copolymer with a non color-forming ethylenic monomer which does not undergo coupling with the oxidation product of an aromatic primary amine developing agent.
  • non color-forming ethylenic monomer which does not undergo coupling with the oxidation product of an aromatic primary amine developing agent, include acrylic acid, a-chloroacrylic acid, ⁇ -alkylacrylic acid (e.g., methacrylic acid), ester or amide derived therefrom (e.g., acrylamide, n-butylacrylamide, t-butylacrylamide, diacetoneacrylamide, methacrylamide, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate, iso-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butylmethacrylate, and a-hydroxy methacrylate), methylene dibisacrylamide, vinyl ester or
  • a high color-forming ballst group described in Japanese Patent Application (OPI) Nos. 42045/1983, 214854/1984, 177553/1984, 177544/1984 or 177557 is applied to any compound represented by formula (XIII) to (XVIII).
  • the coupler of the present invention represented by formula (XII) is added to an emulsion layer in an amount of 2 x 10 -3 mol to 5 x 10 mol, preferably 1 ⁇ 10 mol to x 10 -1 mol, per mol of silver halide included in the same layer. More than one kind of the coupler of the present invention may be added to the same emulsion layer.
  • pyrazoloazole couplers examples include pyrazolobenzimidazole described in U.S. Patent No. 3,369,897, more preferably pyrazolo 5,1-c 1,2,4 triazoles described in U.S. Patent No. 3,725,067, pyrazolotetrazoles described in Research Disclosure, No. 24220 (June 1984), and pyrazolopyrazole described in Research Disclosure, No. 24230 (June 1984).
  • Imidazo 1,2-b pyrazoles, described in European Patent No. 119,741 are preferable
  • pyrazolo 1,5-b 1,2,4 triazoles described in European Patent No. 119,860, are particularly preferable with respect to the reduced yellow side-absorption and fastness of developed dyes on exposure to light.
  • the cyan couplers that can be used in this invention include naphthol couplers and phenol couplers of the oil-protected type.
  • An example of a naphthol coupler is that disclosed in U.S. Patent No. 2,474,293, and preferred examples of naphthol couplers are such two-equivalent naphthol couplers as the oxygen atom splitting-off type disclosed in U.S Patent Nos. 4,052,212, 4,146,396, 4,228,233, and 4,296,200.
  • Examples of the phenol couplers are those disclosed in U.S. Patent Nos. 2,369,929, 2,801,171, 2,772,162, and 2,895,826.
  • cyan couplers stable to moisture and heat examples include phenol cyan couplers having a higher alkyl group than methyl group at the meta position of the phenol nucleus, as disclosed in U.S. Patent No. 3,772,002, 2,5-diacylamino-substituted phenol cyan couplers disclosed in U.S. Patent Nos. 2,772,162, 3,758,308, 4,126,396, 4,334,011, and 4,327,173, German Patent (OLS) 3,329,729 and Japanese Patent Publication No.
  • a preferred alkyl group represented by R' is an alkyl group containing 1 to 32 carbon atoms, e.g., methyl, butyl, tridecyl, cyclohexyl and allyl; an aryl group, including a phenyl and naphthyl; and a heterocyclic group, including 2-pirizyl and 2-furyl.
  • R 1 is a amino group
  • a phenyl-substituted amino group which may have a further substituent is especially preferable.
  • R' may further be substituted by a substituent selected from a group comprising an alkyl group, aryl group, alkyl-or aryi-oxy group (e.g., methoxy, dodecyloxy, methoxyethoxy, phenyloxy, 2,4-di-tert-amyl- phenoxy, 3-tert-butyl-4-hydroxyphenyloxy, or naphthyloxy), carboxy group, alkyl-or aryl-carbonyl group (e g., acethyl, tetradecanoyl, or benzoyl), alkyl-or aryl-oxycarbonyl group (e.g., methoxycarbonyl or phenoxycarbonyl), acyloxy group (e.g, acetyl or benzoyloxy), sulfamoyl group (e.g., N-ethylsulfamoyl or N-octadecylsulfam
  • Z' in formula (XI) represents a hydrogen atom or a coupling-off group, e.g., a halogen atom (e.g., fluorine, chlorine, or bromine), an alkoxy group (e.g , dodecyloxy, methoxycarbamoylmethoxy, carbox- ypropyloxy, or methylsulfonylethoxy), an aryloxy group (e.g., acetoxy, tertradecanoyloxy, or benzoloxy), a sulfonyloxy group (e.g., methanesulfonyloxy or toluensulfonyloxy), an amido group (e.g., dich- loroacetylamino, methanesulfonylamino, or toluenesulfonylamino), an alkoxycarbonyloxy group (e.g., ethox- ycarbonyloxy or
  • R' or R 2 in formula (XI) may form a dimer or polymer.
  • the cyan couplers represented by above-described formula (XI) can be synthesized according to the description in Japanese Patent Application (OPI) No. 166956/1984 and Japanese Patent Publication No. 11572/1974.
  • a magenta coupler of such dye diffusing type is disclosed in U.S. Patent No. 4,366,237 and British Patent No. 2,125,570; and a similar type of yellow magenta, or cyan coupler is disclosed in European Patent No. 96,570 and German Patent (OLS) No. 3,234,533.
  • the dye-forming couplers and the special couplers described above may be dimeric, oligomeric, or polymeric.
  • Examples of polymerized dye-forming couplers are disclosed in U.S. Patent Nos. 3,451,820 and 4,080,211.
  • Examples of polymerized magenta couplers are disclosed in British Patent No. 2,102,173 and U.S. Patent No. 4,367,282.
  • various couplers used in the present invention can be employed as a combination of two or more couplers in a light-sensitive layer, or the same compound can be employed in two or more layers.
  • the couplers to be used in the present invention can be incorporated to photographic materials by various known dispersing processes. Examples of a high-boiling organic solvent for use in the oil-in-water dispersing process are described in U.S. Patent No. 2,322,027. The steps and effect of the latex dispersion method and examples of latex for impregnation are described in U.S. Patent No. 4,199,363 and German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.
  • OLS German Patent Application
  • Couplers to be used in the present invention can be prepared by the method described in Japanese Patent Application No. 49613/1987 or International Application No. PCT/JP/87/00492. In this method at least one oil-soluble coupler which has been made nondiffusible and at least one water-insoluble and organic solvent-soluble homopolymer or copolymer are dispersed into an organic solvent to prepare a dispersion comprising lipophilic fine particles.
  • the polymers used in the preparation method described alone may be any polymers if they consist of repeating units of at least one type having no acid group on the main chain or on the side chain and they are insoluble in water but soluble in organic solvents, it is preferable to use a polymer whose repeating unit has a
  • the repeating unit of the polymer that has no acid group has a group on the main chain or the side chain; or to use silver halide color photographic materials wherein the repeating unit of the polymer that has no acid group has a group in which G 11 and G 12 each represent a hydrogen atom or a substituted or unsubstituted alkyl or aryl group on the side chain.
  • these polymers are applied in such a manner as to be dissolved together with at least one oil-soluble coupler, which has been made non-diffusible, into an organic solvent to be incorporated as a dispersion of fine particles into a coating liquid.
  • at least one oil-soluble coupler which has been made non-diffusible
  • an organic solvent to be incorporated as a dispersion of fine particles into a coating liquid.
  • the size of the fine particles of the dispersion generally the size is 0.05 to 2.0 ⁇ m, preferably 0.05 to 1.0 u.m, and more preferably 0.1 to 0.20 u.m.
  • suitable co-solvents may be used in addition to conventional high-boiling solvents to dissolve the polymers.
  • co-solvents for example, ethyl acetate, butyl acetate, and methyl ethyl ketone.
  • the molecular weight and polymerization degree of the polymers used in this method do not substantially influence the effect of the process, if the molecular weight becomes higher, for example, it will take much time to dissolve the polymer in a co-solvent or the polymer will have difficult, becoming emulsified and dispersed due to the high viscosity of the solution. This results in coarse particles and can cause the color developing property to be reduced and the coating properties to be defective. To overcome this, if a large amount of a co-solvent is used to lower the viscosity of the solution, other process problems will arise.
  • the viscosity of the polymer is such that when 30 g of a polymer is dissolved in 100 m l of a co-solvent the viscosity becomes preferably 5000 cps or below, more preferably 2000 cps or below.
  • the molecular weight of polymers that can be used in the present invention is 150,000 or below, more preferably 80,000 or below, and still more preferably 30,000 or below.
  • the ratio of the polymer to the co-solvent depends on the type of the polymer used, and it can vary widely depending, for example, on the solubility of the polymer in the co-solvent, the polymerization degree of the polymer, and the solubility of the coupler.
  • a co-solvent is used in such a amount that the solution containing at least the coupler, the high-boiling coupler solvent, and the polymer in the co-solvent has a viscosity low enough to cause the solution to be readily dispersed in water or an aqueous hydrophilic colloid solution.
  • the proportion of the polymer of the present invention to the coupler is preferably 1 : 20 to 20 : 1, more preferably 1 : 10 to 10 : 1 (weight ratio).
  • Examples of polymers may be used in the method above described are as follows:
  • the dispersion can be prepared as follows:
  • This dispersing method is preferable in view of attaining further improvement of the antifading property of the color image and to prevent fluctuation in the photographic properties during the processing process.
  • the color couplers are used in an amount of 0.001 to 1 mol per mol of photosensitive silver halides.
  • the preferred amounts of coupler are 0.01 to 0.5 mol for yellow coupler 0.003 to 0.3 mol for magenta coupler, and 0.02 to 0.3 mol for cyan coupler.
  • the photographic materials to be used in the present invent on are those applied on usual flexible bases such as plastics films (e.g., cellulose nitrate, cellulose acetate, or polyethyleneterephtalate), paper, or on a rigid base such as a glass plate.
  • plastics films e.g., cellulose nitrate, cellulose acetate, or polyethyleneterephtalate
  • a rigid base such as a glass plate.
  • a reflective base may be preferably used.
  • the "reflective base” can increase the reflectivity and make clear the dye image formed in a silver halide emulsion layer.
  • Such a reflective base includes a base coated with a hydrophobic resin that contains a light reflecting material such as titanium oxide, zinc oxide, calcium carbonate, and calcium sulfate.
  • a processing solution having the following composition was prepared.
  • A-multi-layer color photographic paper was prepared which has such layers as hereinbelow described on a paper laminated on both sides with polyethylene.
  • Coating solutions were prepared as follows: Preparation of the first layer coating solution
  • the undermentioned blue-sensitive sensitizing dye was added to a silver chlorobromide emulsion (containing 1.0 mol% of silver bromide and 70 g/kg of Ag), the amount being 5.0 x 10 -4 mol per mol of silver chlorobromide.
  • This blue-sensitive emulsion was mixed with and dissolved in the above emulsified and dispersed solution so as to obtain the composition shown below, thereby constituting the desired first coating solution.
  • the second to seventh layer coating solutions were prepared in the same manner as the first.
  • As a gelatin hardner for the respective layers 1-oxy-3,5-dichloro-s-triadine sodium salt was used.
  • Blue-sensitive emulsion layer (5.0 x 10 -4 mol per mol of a silver halide) Green-sensitive emulsion layer (4.0 x 10-4 mol per mol of a silver halide) and (7.0 x 10-5 mol per mol of a silver halide) Red-sensitive emulsion (0.9 x 10 x 10-4 mol per mol of a silver halide)
  • the following compound was added to the red-sensitive emulsion layer in amount of 2.6 x 10 -3 mot per mol of a silver halide.
  • 1-(5-methylureidophenyl)-5-mercapto-tetrazole was added to the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer in amounts of 8.5 x 10 -5 mol, 7.7 x 10 mol and 2.5 x 10 mol per mol of a silver halide, respectively.
  • each layer is shown below. Each ingredient is indicated in g/m 2 of a coating amount, but the coating mount of silver halide emulsion is shown in g/m 2 in terms of silver.
  • Polyethylene laminated paper a white pigment, TiO 2 and bluish dye, ultramarine, were included in the first layer side of the polyethylene film laminated).
  • the obtained color photographic paper was exposed through an optical wedge and then processed through the following processing steps:
  • rinsing solutions were used in a four-tank counter-current washing system from the above rinsing 4 to rinsing 1. Processing solutions which were used in the above steps were as follows:
  • the photographic characteristics were represented with 2 points of Dmin and the gradation of magenta concentration.
  • the Dmin was indicative of the minimum concentration, and the gradations denoted by the concentration change between a point of a concentration of 0.5 to a point of concentration corresponding to a point higher on the exposure side of 0.3 in terms of logE.
  • a multi-layer color photographic paper was prepared which has such layers as hereinbelow described on a paper laminated on both sides with polyethylene. Coating solutions were prepared as follows:
  • Example 2 The same procedure as in Example 2 was repeated with the exception of using an image dye stabilizer (Cpd) and a silver chlorobromide emulsion containing 80.0 mol% of silver bromide and 70 g/kg of Ag.
  • image dye stabilizer Cpd
  • a silver chlorobromide emulsion containing 80.0 mol% of silver bromide and 70 g/kg of Ag.
  • Example 2 The same compounds as Example 2 were used.
  • 1-(5-methylureidophenyl)-5-mercaptotetrazole was added to the blue-sensitive emulsion layer, the green-sensitive emulsion layer, and the red-sensitive emulsion layer in amounts of 4.0 x 10 -6 mol, 3.0 x 10 -5 mol and 1.0 x 10 -5 mol per mol of a silver halide, respectively.
  • 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer in amounts of 1.2 x 10 mol and 1.1 x 10 mol per mol of a silver halide, respectively.
  • each layer is shown below.
  • the figures represent coating amounts (g/m 2 ).
  • the coating amount of each silver halide emulsion is represented in terms of silver.
  • Second Layer Color mix inhibiting layer
  • the above-mentioned photographic material was subjected to a running test, altering the composition of the color developing solution and replenisher amount of the rinsing solution, until the color developing solution twice as much as the volume of a tank had been replenished.
  • composition of each processing solution was as follows:
  • each paper to both surfaces of which polyethylene films had been laminated and which had been subjected to corona discharge processing, was coated in turn with the first layer (bottom layer) to the seventh layer (top layer) in order to form photographic paper samples.
  • a coating solution of each layer was prepared by the following procedure. In this connection structural formulae and others of the couplers, dye stabilizers and the like used in the coating solutions will be described hereinafter.
  • the coating solution of the first layer was prepared as follows: Six hundred milliliters of ethyl acetate as a co-solvent was added to a mixture of 200 g of a yellow coupler, 93.3 g of a color mix inhibitor (r), 10 g of a high-boiling solvent (p), and 5 g of a solvent (q), and the mixture was then heated to 60°C to dissolve the respective components. Afterward the mixture was added to 3,300 mi of a 5% aqueous gelatin solution containing 330 m l of a 5% aqueous solution of Alkanol B (trade name, alkylnaphthalene- sulfonate, Du Pont).
  • this solution was emulsified by the use of a colloid mill to prepare a coupler dispersion. From this dispersion ethyl acetate was distilled off, and the dispersion was further added to 1,400 g of an emulsion containing, in addition to 96.7 g of Ag and 170 g of gelatin, a sensitizing dye for a blue-sensitive emulsion layer and 1-methyl-2-mercapto-5-acetylamino-1,3,4-triazole. Moreover, 2,600 g of a 10% aqueous gelatin solution was added thereto, thus preparing a coating solution. Coating solutions for the second to the seventh layers were prepared in accordance with the compositions shown in Table B in the same manner as for the first layer.
  • the cyan couplers for the fifth layer are shown in the following Table 4, in order to prepare photographic papers.
  • 1,2-Bis(vinylsulfonyl)ethane was used as a hardening agent.
  • the following compounds were used as couplers.
  • Multi-layer color photographic papers were prepared by forming the following layer structures on each paper base that had been laminated on both sides with polyethylene. Coating solutions were prepared by mixing emulsions, various chemicals and coupler emulsions with one another, followed by dissolving, as follows:
  • Yellow coupler emulsion was prepared in the same procedure of Example 2.
  • the following dye was added to prevent the respective emulsion layers for irradiation.
  • the following compound was added in amount of 2.6 x 10 mol per of a silver halide.
  • Emulsions used in this Example were as follows:
  • Green-sensitive Emulsion Silver chloride grains containing K 2 IrCl 6 and 1,3-dimethylimidazoline-2-thione were prepared in the usual way, and a sensitizing dye (S-2) was added thereto in a ratio of 4 x 10 mol per mol of Ag. KBr was further added thereto, and after ripening, sodium thiosulfate was added thereto and optimum chemical sensitization was then achieved. A stabilizer (Stb-1) was added thereto in a ratio of 5 x 10 mol per mol of Ag in order to prepare a monodisperse cubic silver chloride emulsion having an average grain size of 0.48 um and a coefficient of variation of 0.10.
  • Red-sensitive Emulsion The same procedure as for the green-sensitive emulsion was repeated with the exception that a sensitizing dye (S-3) was substituted for (S-2) in a ratio of 1.5 x 10 mol per mol of Ag, in order to prepare a red-sensitive emulsion.
  • S-3 a sensitizing dye
  • composition of the respective layers in the sample were as follows. Figures represent coating amounts (g/m 2 ). The amount of each silver halide emulsion was represented by a coating amount in terms of silver.
  • Second layer Color mix inhibitor
  • 1-Oxy 3,5-dichloro-s-triazine sodium salt was used as a hardening agent for each layer.
  • a multi-layer color photographic paper was prepared which has such layers as hereinbelow described on a paper laminated on both sides with polyethylene. Coating solutions were prepared as follows:
  • Each of the undermentioned emulsions EM1 and EM2 was mixed with the above-obtained emusified and dispersed solution and dissolved, and the concentration of gelatin in the mixture was adjusted so as to obtain the composition shown below, thereby preparing the first coating solution.
  • the second to the seventh layer coating solutions were prepared in the same maner as the first coating solution.
  • As a gelatin hardner for the respective layers the sodium salt of 1-oxy-3,5-dichloro-2-triazine was used.
  • a thickener a compound (Cpd-2) was used.
  • each layer is shown below. Each ingredient is indicated in g/m 2 of a coating amount, but the coating amount of silver halide is shown in g/m 2 in terms of silver.
  • Polyethylene laminated paper (a white pigment, TiO 2 and a bluish dye, ultramarine, were included in the first layer side of the polyethylene film laminated).
  • First layer Blue-sensitive layer Monodisperse silver chlorobromide emulsion (EM1) spectral-sensitized by sensitizing dye (ExS-1) 0.13
  • Green-sensitive emulsion layer Monodisperse silver chlorobromide emulsion (EM3) spectral-sensitized by sensitizing dye (ExS-2,-3) 0.05
  • Red-sensitive emulsion layer Monodisperse silver chlorobromide emulsion (EM5) spectral-sensitized by sensitizing dye (ExS-4,-5) 0.07
  • the dyes (Cpd-13 and -14) were used.
  • Alkanol XC (tradename, made by Dupont) and sodium alkylenzenesulfonate were used as auxiliary agents for emulsification and dispersion, and succinate ester and Magnefac F-120 (tradename, made by Dainippon Ink) were added as coating aids to each layer. Further, Cpd-15 and Cpd-16 were used as stabilizers for the layers containing silver halide.
  • the silver halide emulsion used in this Example were as follows:
  • compositions of the processing solution were as follows:
  • the change of photographic characteristics was slight, and in particular, when benzyl alcohol was not present, and when sulfite salt was not present, the effects of this invention were more remarkable.
  • Example 7 The same procedure as Test No. 2 in Example 7 was repeated except that the magenta coupler M-37 was changed to M-9, M-44, M-45, M-47, M-52, M-57 and M-58, respectively. The same significant improvement as in Example 7 were attained.

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EP88102484A 1987-02-20 1988-02-19 Method for processing silver halide color photographic materials and color photographic developing composition Withdrawn EP0279464A3 (en)

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JP62037351A JPS63204258A (ja) 1987-02-20 1987-02-20 ハロゲン化銀カラ−写真感光材料の処理方法
JP37351/87 1987-02-20
JP115947/87 1987-05-14
JP11594787A JPH01105247A (ja) 1987-03-06 1987-05-14 ハロゲン化銀カラ−写真感光材料の処理方法

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0602749A1 (de) * 1992-12-18 1994-06-22 Eastman Kodak Company Photographisches Material und Verfahren enthalten einen bicyclischen Pyrazolokuppler
EP0710876A1 (de) 1994-11-02 1996-05-08 Minnesota Mining And Manufacturing Company Photographische Schwarz-Weiss-Elemente

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06105346B2 (ja) * 1986-11-07 1994-12-21 富士写真フイルム株式会社 ハロゲン化銀カラ−写真感光材料の処理方法

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0602749A1 (de) * 1992-12-18 1994-06-22 Eastman Kodak Company Photographisches Material und Verfahren enthalten einen bicyclischen Pyrazolokuppler
US5811230A (en) * 1992-12-18 1998-09-22 Eastman Kodak Company Photographic material comprising a bicyclic pyrazolo coupler
EP0710876A1 (de) 1994-11-02 1996-05-08 Minnesota Mining And Manufacturing Company Photographische Schwarz-Weiss-Elemente

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