Classifications

• • 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 of processing light-sensitive silver halide color photographic material. More particularly it relates to a technique for stabilizing photographic performances in color processing in which the amount of replenishment has been decreased.
• Light-sensitive silver halide color photographic materials are processed basically through two steps of color development and desilvering.
• the desilvering is comprised of the steps of bleaching and fixing or the step of bleach-fixing. Besides these, rinsing and stabilizing are added as additional processing steps.
• Developing solutions are regenerated by removing unwanted accumulated components, i.e., matters dissolved out from light-sensitive materials, and supplying the components having run short.
• This method (including the ion-exchange resin process and the electrodialysis), however, has a disadvantage such that the development processing performances of light-sensitive materials may be damaged unless the quantities of components in a developing solution are determined by chemical analysis so as to be made constant, and requires a complicated management. Hence, it is almost impossible for this method to be employed in small-scale finishing laboratories or mini-labs having no particular skills. This method also has the disadvantage that it requires a very high initial cost.
• the method in which a regenerant is added to an overflowing solution so that it can be again used as a replenishing solution has the disadvantage that it requires a space for stock tanks, etc. or is cumbersome for the finishing laboratories to handle. Hence, it is very difficult for this method also to be employed in mini-labs or the like.
• the concentrated low-replenishing method can be said to be very suited for small-scale finishing laboratories (or mini-labs) where processing is carried out in a small quantity, since this method requires no particular additional apparatus and processing can be managed with ease.
• the concentrated low-replenishing method however, also has some problems. That is, it has the problems that a decrease in maximum density, a decrease in gamma and a decrease in sensitivity may become extraordinary with an increase in the accumulation of organic restrainers dissolved out of light-sensitive materials and the accumulation of hydrogen ions that are released as a result of development reaction.
• an object of the present invention is to provide a technique for stabilizing photographic performances when light-sensitive silver halide color photographic material are processed by the low-replenishing method, in particular, when they are processed in a small processing quantity in a discontinuous manner, stated specifically, to provide a method of processing a light-sensitive silver halide color photographic material, that can obtain a stable color-forming performance, i.e., maximum density, can give less fog density and also may cause less variations of gradation.
• the above object of the present invention can be achieved by a method of processing a light-sensitive silver halide color photographic material, comprising processing said light-sensitive silver halide color photographic material by the use of a color developing solution containing at least a chloride in a concentration of not less than 6 x 10 ⁇ 2 mol/lit. and a buffering agent with a pKa of not less than 10.5, and at a temperature of not lower than 38°C.
• Preferred embodiments of the present invention can be exemplified by the following embodiments (1) to (4), according to which the object of the present invention can be more highly achieved.
• the chloride incorporated in the color developing solution of the present invention may include chlorides of alkali metals, as exemplified by potassium chloride, sodium chloride and lithium chloride, any of which can be preferably used. It may be contained in an amount, as described above, of not less than 6 x 10 ⁇ 2 mol/lit., and preferably in an amount corresponding to the range of 8 x 10 ⁇ 2 mol/lit. ⁇ [Cl ⁇ ] ⁇ 2.0 x 10 ⁇ 1 mol/lit.
• the buffering agent referred to in the present invention means a substance having a resistance to changes in the concentration of hydrogen ions in the solution.
• buffering agents an agent with a pKa of not less than 10.5 is added to the color developing solution.
• the object of the present invention can be thereby well achieved. They can also be used in combination of two or more kinds.
• the buffering agent preferably usable in the present invention may include the following buffering agents having a pKa value of 10.5 or more. These buffering agents may be used in the form of salts such as a sodium salt and a potassium salt.
• the buffering agent incorporated in the color developing solution of the present invention has a pKa of not less than 10.5 as stated above. It may preferably be those with a pKa of 11.0 to 13.0, and most preferably be phosphoric acid.
• hydroxylamine derivatives as disclosed in Japanese Patent Publications Open to Public Inspection (hereinafter referred to as Japanese Patent O.P.I. Publication(s)) No- 146043/1988, No. 146042/1988, No. 146041/1988, No. 146040/1988, No. 135938/1988 and No. 118748/1988, hydroximic acids as disclosed in Japanese Patent O.P.I. Publication No.
• hydrazines hydrazides, phenols, ⁇ -hydroxyketones, ⁇ -aminoketones, saccharides, monoamines, diamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, condensed ring type amines are preferably used as organic preservatives in place of hydroxylamines conventionally used as preservatives
• incorporation of a compound represented by the following formula A or B brings about a preferable result for rapid processing and for a decrease in bluing, and also a good result with regard to the deposition of tar on the wall surface of a color developing solution tank. It can also be effective from other aspects, and hence can be said to be one of more preferred embodiments of the present invention.
• R1 and R2 each represent a hydrogen atom, an alkyl group, an aryl group, R′-CO-, provided that both are not hydrogen atoms at the same time.
• the alkyl groups represented by R1 and R2 may be the same or different, and each may preferably be an alkyl group having 1 to 3 carbon atoms.
• R′ represents an alkoxyl group, an alkyl group or an aryl group.
• the alkyl groups represented by R1, R2 and R′ may include those having a substituent.
• R1 and R2 may combine each other to form a ring. For example, they may form a heterocyclic ring such as piperidine, pyridine, triazine or morpholine.
• R3, R4 and R5 each represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group
• R6 represents a hydroxyl group, a hydroxylamino group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkoxyl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted carbamoyl group, or an amino group.
• the heterocyclic group is a ring of 5 to 6 members, constituted of e.g., C, H, O, N and S, and may be saturated or unsaturated.
• R6 represents a group selected from an alkyl group, an aryl group and a heterocyclic ring.
• R5 and R6 may combine to form a heterocyclic ring.
• R3, R4 and R5 may each preferably be a hydrogen atom or an alkyl groups having 1 to 10 carbon atoms.
• R3 and R4 are most preferably hydrogen atoms.
• R6 may preferably be an alkyl group, an aryl group, a carbamoyl group or an amino group. In particular, it is preferably an alkyl group or a substituted alkyl group.
• preferred substituents of the alkyl group are a carboxyl group, a sulfo group, a nitro group, an amino group, a phosphono group, etc.
• These compounds represented by the formula A or B are usually used in the form of free amines, hydrochlorides, sulfates, p-toluenesulfonates, oxalates, phosphates, acetates or the like.
• the compound represented by the above formula A or B may be contained in the color developing solution in a concentration of usually 0.2 g/lit. to 50 g/lit., preferably 0.5 g/lit. to 30 g/lit., and more preferably 1 g/lit. to 15 g/lit.
• the compound represented by the formula A or B can be used in combination with a conventionally used hydroxylamine and the organic preservative previously described. In view of developability, it is preferred not to use the hydroxylamine.
• R8 represents a hydroxyalkyl group having 2 to 6 carbon atoms
• R9 and R10 each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 2 to 6 carbon atoms, a benzyl group or a group represented by the formula: wherein n′ represents an integer of 1 to 6,
• X and Y each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group having 2 to 6 carbon atoms.
• a and B each represents a straight-chain or branched alkylene group, and n ⁇ and m each represent an integer of 0 to 100, provided that n ⁇ and m are not 0 at the same time.
• Preferred examples of the compound represented by the formula D are as follows: D-1 HO-CH2CH2-OH D-5 HO-CH2CH2CH2-OH D-11 HO-CH2CH2CH2CH2-OH D-18 HO-CH2CH2-O-CH2CH2-OH D-24 HO-CH2CH2CH2-O-CH2CH2-OH D-25 HO-CH2CH2CH2-O-CH2CH2CH2-OH
• the compound represented by the formula C or D may preferably be used in an amount ranging from 1 g to 100, and more preferably 2 g to 50 g, per liter of the color developing solution from the view point of preventing air oxidation.
• the color developing agent used in the color developing solution of the present invention may preferably be a p-phenylenediamine compound having a water-soluble group.
• at least one water-soluble group is present on the amino group or benzene ring of the p-phenylenediamine compound.
• a specific water-soluble group may preferably include;
• those preferably used in the present invention are the compounds represented by the compound Nos. (DA-1), (DA-2), (DA-3), (DA-4), (DA-6), (DA-7) and (DA-15). Particularly preferred is the compound No. (DA-1).
• the color developing agents described above are usually used in the form of salts such as hydrochlorides, sulfates and p-toluenesulfonates.
• the preferably usable p-phenylenediamine compound having the water-soluble group is required to be in an amount of not less than 4.5 x 10 ⁇ 3 mol, and preferably in an amount ranging from 6.5 x 10 ⁇ 3 mol to 3.4 x 10 ⁇ 2 mol, per liter of the color developing solution.
• the color developing solution used in the present invention may contain the following developing solution components.
• Inorganic or organic antifoggants can be optionally added.
• a development accelerator can also be optionally used.
• the development accelerator may include various pyridinium compounds as typically disclosed in U.S. Patents No. 2,648,604 and No. 3,671,247 and Japanese Patent Examined Publication No. 9503/1969, and other cationic compounds; cationic dyes such as phenosafranine; neutral salts such as thallium nitrate; polyethylene glycol and derivatives thereof as disclosed in U.S. Patents No. 2,533,990, No. 2,531,832, No. 2,950,970 and No. 2,577,127 and Japanese Patent Examined Publication No 9504/1969; nonionic compounds such as polythioethers; phenethyl alcohol as disclosed in U.S. Patent No. 2,304,925; and besides acetylene glycol, methyl ethyl ketone, dichlorohexanone, thioethers, pyridine, ammonia, hydrazine, and amines.
• cationic dyes such as phenosafranine
• Benzyl alcohol is not preferably used in the present invention.
• sparingly soluble organic solvents as typified by the above phenethyl alcohol it is preferred for them not to be used in order to efficiently achieve the stated object of the present invention.
• benzyl alcohol tends to result in the formation of tar when the color developing solution is used over a long period of time, in particular, in running processing carried out according to the low-replenishing method.
• the tar thus formed may adhere to paper light-sensitive materials being processed, even to cause a serious trouble that their commercial values are seriously damaged.
• the sparingly soluble organic solvents have a poor solubility in water. Hence, not only they make it necessary to take the trouble to use a stirrer to prepare the color developing solution itself, but also even the use of such a stirrer can not avoid a limit in the effect of accelerating development, because of its poorness in solubility.
• the sparingly soluble organic solvents have a large value for the burden of environmental pollution, as exemplified by the biological oxygen demand (BOD), and can not be thrown away in drainage or rivers. Thus, much labor and cost are required for the disposal of waste liquor. Because of such problems, not only benzyl alcohol but also other sparingly soluble organic solvents should preferably be used in quantities as small as possible or be not used.
• the color developing solution of the present invention may preferably contain a triazinylstilbene fluorescent brightening agent.
• the triazinylstilbene fluorescent brightening agent may include those represented by the following formula E.
• X1, X2, Y1 and Y2 each represent a hydroxyl group, a halogen atom such as chlorine or bromine, an alkyl group such as methyl or ethyl, an aryl group such as phenyl or methoxyphenyl,
• R21 and R22 each represent a hydrogen atom, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group
• R23 and R24 each represent a substituted or unsubstituted alkylene group
• R25 represents a hydrogen atom, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.
• M represents a cation as exemplified by sodium, potassium, lithium or ammonium.
• the alkyl group represented by R21, R22 and R25 may preferably be an alkyl group having 1 to 6 carbon atoms.
• the alkylene group represented by the above R23 and R24 may preferably be an alkylene group having 1 to 2 carbon atoms.
• Substituents on the alkyl group and aryl group represented by the above R21, R22 and R25 and the alkylene group represented by the above R23 and R24 may preferably include a hydroxyl group, a sulfo group, a sulfoamino group and a carboxyamino group.
• Examples of the group may be an amino group, an alkylamino group as exemplified by methylamino, ethylamino, propylamino, dimethylamino, cyclohexylamino, ⁇ -hydroxyethylamino, di( ⁇ -hydroxyethyl)amino, ⁇ -sulfoethylamino, N-( ⁇ -sulfoethyl)-N-methylamino or N-( ⁇ -hydroxyethyl-N-methylamino, and an arylamino group as exemplified by anilino, o-, m- or p-sulfoanilino, o-, m-or p-chloroanilino, o-, m- or p-toluidino, o-, m- or p-carboxyanilino, o-, m- or p-hydroxyanilino, sufona
• An example of the group may be a morpholino group
• examples of the group -OR25 may be an alkoxyl group as exemplified by methoxy, ethoxy or methoxyethoxy, an aryloxy group as exemplified by phenoxy or p-sulfophenoxy.
• a preferred compound is a compound wherein all the X1, X2, Y1 and Y2 are each A most preferred compound is a compound wherein one of X2 and Y1 is -OR25 and the other is and when one of X2 and Y2 is -OR25 the other is
• the triazinylstilbene fluorescent brightening agent preferably used in the present invention can be synthesized by any conventional methods as disclosed, for example, in "Fluorescent Brightening Agents", Edited by KASEIHIN KOGYO KYOKAI, published August, 1976, page 8.
• the triazinylstilbene fluorescent brightening agent may preferably be used in an amount ranging from 0.2 g to 10 g, and more preferably from 0.4 g to 5 g, per liter of the color developing solution.
• any of methyl cellosolve, methanol, acetone, dimethylformamide, ⁇ -cyclodextrin and besides the compounds disclosed in Japanese Patent Examined Publications No. 33378/1972 and No. 9509/1969 can be used as an organic solvent used to increase the solubility of developing agents.
• auxiliary developing agents include, for example, N-methyl-p-aminophenol hexasulfate (Metol), phenidone, N,N-diethyl-p-aminophenol hydrochloride, and N,N,N′,N′-tetramethyl-p-phenylenediamine hydrochloride, which may preferably be added usually in an amount of 0.01 g/lit. to 1.0 g/lit.
• Metal N-methyl-p-aminophenol hexasulfate
• phenidone N,N-diethyl-p-aminophenol hydrochloride
• N,N,N′,N′-tetramethyl-p-phenylenediamine hydrochloride which may preferably be added usually in an amount of 0.01 g/lit. to 1.0 g/lit.
• a chelating agent represented by the following formula K is added to the color developing solution of the present invention a chelating agent represented by the following formula K.
• E represents a substituted or unsubstituted alkylene, cycloalkylene, phenylene group, -R15OR15-, -R15OR15OR15- or -R15ZR15.
• Z represents R11 to R15 each represents a substituted or unsubstituted alkylene group.
• A1 to A5 each represent a hydrogen atom, -OH, -COOM or -PO3(M)2.
• M represents a hydrogen atom or an alkali metal atom.
• the color developing solution of the present invention may still also contain an anionic, cationic, amphoteric or nonionic surface active agent.
• All the components for the above color developing solution may be used by successively adding them to a given amount of water.
• the components with a low solubility to water can be added by mixing them with the organic solvent previously described such as triethanolamine.
• a plurality of components that can be present together stably one another may be previously made into an aqueous conc. solution or in the state of solids put in a small container, which may be added to water followed by stirring so that the resulting solution can be used as the color developing solution of the present invention.
• the above color developing solution may be used at and desired pH range. From the viewpoint of rapid processing, it is preferably used at pH 9.5 to 13.0, and more preferably at pH 9.8 to 12.0.
• the processing temperature is not lower than 38°C, preferably 38.3°C to 43.0°C, and particularly preferably 39°C to 41°C.
• the processing time may preferably be within 90 seconds, more preferably 3 seconds to 60 seconds, and particularly preferably 5 seconds to 45 seconds.
• the color developing solution should be replenished preferably in an amount of not more than 120 ml/m2, more preferably 20 ml/m2 to 100 ml/m2, and particularly preferably 25 ml/m2 to 70 ml/m2.
• various processing methods can be used, including the monobath processing and other various methods as exemplified by the spray method in which the processing solution is sprayed, the web method in which a light-sensitive material is brought into contact with a carrier impregnated with the processing solution, and a developing method making use of a viscous processing solution.
• the color development processing is followed by bleaching and fixing or monobath bleach-fixing.
• the monobath bleach-fixing is preferably used.
• a bleach-fixing solution used in the monobath bleach-fixing will be described below in detail.
• an organic acid ferric complex salt such as aminopolycarboxylic acid
• An organic acid that forms the organic acid ferric complex salt may preferably include an aminocarboxylic acid compound and an aminophosphonic acid compound, which respectively refers to an amino compound having at least one carboxylic acid group and an amino compound having at least one phosphonic acid group. They are more preferably be the compounds represented by the following formulas (1) and (2).
• E represents a substituted or unsubstituted alkylene group, a cycloalkylene group, a phenylene group, -R55OR55OR55- or -R55ZR55.
• Z represents R51 to R55 each represent a substituted or unsubstituted alkylene group.
• A1 to A5 each represent a hydrogen atom, -OH, -COOM or -PO3M2, wherein M represents a hydrogen atom or an alkali metal atom.
• aminocarboxylic acid compounds and aminophosphonic acid compounds compounds particularly preferably used in view of the effect for the object of the present invention include the following: (1-1), (1-2), (1-4), (1-5), (1-6), (1-7), (1-8), (1-10), (1-19), (2-1), (2-3) and (2-5).
• aminocarboxylic acid compounds and aminophosphonic acid compounds particularly preferred compounds are compounds (1-1), (1-2), (1-4) and (1-8) because of their high bleaching performance and feasibility for rapid processing.
• At least one of these ferric complex salts may be used. Two or more kinds of them may also be used in combination.
• bleaching agents should preferably be used in an amount of 5 g/lit. to 450 g/lit., and more preferably 20 g/lit. to 250 g/lit. From the viewpoints of the rapid processing and the effect of preventing stain, it should be used particularly preferably in an amount of 80 g/lit. or more, and most preferably 100 g/lit. to 250 g/lit.
• a solution so composed as to contain, in addition to the bleaching agent described above, a silver halide fixing agent and optionally a sulfite as a preservative is applied to the bleach-fixing solution. It is also possible to use a special bleach-fixing solution so composed as to be in combination of an iron (III) ethylenediaminetetraacetic acid complex bleaching agent and a large quantity of silver halide such as ammonium bromide.
• silver halide besides the ammonium bromide, it is also possible to use hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, etc.
• the above silver halide fixing agent contained in the bleach-fixing solution is a compound capable of forming a water-soluble complex salt as a result of reaction with a silver halide, as used in usual fixing, which is typically exemplified by thiosulfates such as potassium thiosulfate, sodium thiosulfate and ammonium thiosulfate, thiocyanates such as potassium thiocyanate, sodium thiocyanate and ammonium thiocyanate, thioureas, and thioethers. As a preferred example, it is effective to use ammonium salts as having a high diffusion rate to gelatin layers. Any of these fixing agents may be used in an amount not less than 5 g/lit. and within the range it can be dissolved. In usual instances, the fixing agent is used in an amount of 70 g/lit. to 250 g/lit, and preferably 100 g/lit. to 250 g/lit. in view of rapid processing.
• bleach-fixing solution it is also possible to incorporate, alone or in combination, various pH adjusters such as boric acid, borax, sodium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate and ammonium hydroxide.
• various pH adjusters such as boric acid, borax, sodium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate and ammonium hydroxide.
• fluorescent brightening agents antifoaming agents or surface active agents. It is also possible to appropriately incorporate a preservative such as hydroxylamine, hydrazine or an addition product of a bisulfite addition compound of an aldehyde compound, an organic chelating agent such as aminocarboxylic acid, a stabilizer such as nitroalcohol or a sulfate, and an organic solvent such as methanol, dimethylsulfonamide or dimethylsulfoxide.
• a preservative such as hydroxylamine, hydrazine or an addition product of a bisulfite addition compound of an aldehyde compound, an organic chelating agent such as aminocarboxylic acid, a stabilizer such as nitroalcohol or a sulfate, and an organic solvent such as methanol, dimethylsulfonamide or dimethylsulfoxide.
• bleach-accelerators can be added, including those disclosed in Japanese Patent O.P.I. Publication No. 280/1971, Japanese Patent Examined Publications No. 8506/1970 and No. 556/1971, Belgian Patent No. 770,910, Japanese Patent Examined Publications No. 8836/1970 and No. 9854/1978, Japanese Patent O.P.I. Publications No. 71634/1979 and No. 42394/1974, etc.
• the bleach-fixing solution is commonly used at a pH of not less than 4.0 and not more than 9.5, and should preferably be used at a pH of not less than 4.5 and not more than 8.5. Stated more strictly, the bleach fixing is carried out most preferably at a pH of not less than 5.0 and not more than 8.0.
• the bleach-fixing solution is used at a processing temperature of not lower than 80°C, and preferably not lower than 35°C and not higher than 70°C, under control on evaporation or the like. A temperature higher than 70°C is not preferable in view of drying performance. A temperature lower than 35°C is not preferable in view of rapid processing.
• the processing time for bleach fixing may preferably be 2 seconds to 50 seconds, more preferably 3 seconds to 40 seconds, and most preferably 5 seconds to 30 seconds.
• the stabilizing solution may preferably contain a sulfite.
• the sulfite may be any of an organic salt or an inorganic salt so long as it can release sulfite ions. It is preferably an inorganic salt. As preferred specific compounds, it may include sodium sulfite, potassium sulfite, ammonium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, sodium metabisulfite, potassium metabisulfite, ammonium metabisulfite and hydrosulfite.
• the above sulfite may preferably be added in such an amount that may be at least 1 x 10 ⁇ 3 mol/lit., and more preferably be added in such an amount that may range from 5 x 10 ⁇ 3 mol/lit. to 10 ⁇ 1 mol/lit., in the stabilizing solution. Its addition in such an amount can be effective for the present invention, in particular, effective for preventing stain, and is preferably employed in the embodiments of the present invention. As methods for its addition, it may be directly added to the stabilizing solution, or may preferably be added to a stabilizing replenishing solution.
• ammonium compounds may include ammonium compounds. These are fed by ammonium salts of various inorganic compounds, specifically including ammonium hydroxide, ammonium bromide, ammonium carbonate, ammonium chloride, ammonium hypophosphite, ammonium phosphate, ammonium phosphite, ammonium fluoride, ammonium acid fluoride, ammonium fluoroborate, ammonium arsenate, ammonium hydrogencarbonate, ammonium hydrogen fluoride, ammonium hydrogen sulfide, ammonium sulfate, ammonium iodide, ammonium nitrate, ammonium pentaborate, ammonium acetate, ammonium adipate, ammonium laurintricarboxylate, ammonium benzoate, ammonium carbamate, ammonium citrate,a ammonium diethyldithiocarbamate, ammonium formate, ammonium hydrogenmal
• the ammonium compound may be added in an amount preferably ranging from 0.001 mol to 1.0 mol, and more preferably ranging from 0.002 mol to 2.0 mols.
• the stabilizing solution it is particularly preferred for the stabilizing solution to contain a chelating agent having a chelate stability constant with respect to iron ions, of not less than 8.
• the chelate stability constant refers to the constant commonly known from L.G. Sillen and A.E. Martell, "Stability Constants of Metal-ion Complexes", The Chemical Society, London (1964), and S. Chaberek and A.E. Martell, "Organic Seqestering Agents", Wiley (1959).
• the chelating agent having a chelate stability constant with respect to iron ions, of not less than 8 may include organic carboxylic acid chelating agents, organic phosphoric acid chelating agents, inorganic phosphoric acid chelating agents and polyhydroxyl compounds.
• the above iron ions are meant by ferric irons (Fe3+).
• Specific chelating agents having a chelate stability constant with respect to iron ions, of not less than 8 can be exemplified by the following compounds, without limitation thereto. That is, they are ehtylenediaminediorthohydroxyphenylacetic acid, diaminopropanetetraacetic acid, nitrilotriacetic acid, N-hydroxyethylethylenediaminetetraacetic acid, dihydroxyethylglycine, ethylenediaminediacetic acid, ethylenediaminedipropionic acid, iminodiacetic acid, diethylenetriaminepentaacetic acid, hydroxyiminodiacetic acid, diaminopropanoltetraacetic acid, transcyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, ethylenediaminetetrakismethylenephosphonic acid, nitrilotrimethylenephosphonic acid, 1-hydroxyethylidene-1,1-di
• diethylenetriaminepentaacetic acid nitrilotriacetic acid
• nitrilotrimethylenephosphonic acid 1-hydroxyethylidene-1,1-diphosphonic acid, etc.
• 1-hydroxyethylidene-1,1-diphosphonic acid is most preferably used.
• the above chelating agent may be used preferably in an amount of 0.01 g to 50 g, and more preferably 0.05 g to 20 g, per liter of the stabilizing solution, within the range of which good results can be obtained.
• polyvinylpyrrolidone such as PVP K-15, k-30 and K-90
• organic acid salts such as citrates, acetates, succinates, oxalates and benzoates
• pH adjusters such as phosphates, borates, hydrochlorides and sulfuric acid
• mildewproofing agents such as phenol derivatives, catechol derivatives, imidazole derivatives, triazole derivatives, thiabenzole derivatives, organic halogen compounds, and other mildewproofing agents known as slime control agents used in paper-pulp industries
• fluorescent brightening agents surface active agents, antiseptic agents, and salts of metals such as Bi, Mg.
• Zn, Ni, Al, Sn, Ti and Zr Any of these compounds may be used in any combination so long as they are necessary for maintaining the pH of the stabilizing bath and also do not adversely affect the stability required when color photographic images are stored, and the generation of precipitates.
• the processing temperature may range from 15°C to 70°C, and preferably from 20°C to 55°C.
• the processing time may preferably be not more than 120 seconds, more preferably 3 seconds to 90 seconds, and most preferably 6 seconds to 50 seconds, within which the effect of the present invention can be better obtained.
• the soluble iron salt may include inorganic iron salts such as ferric chloride, ferrous chloride, ferric phosphate, ferric bromide, ferric nitrate and ferrous nitrate, and organic acid iron salts such as ferric ethylenediaminetetraacetate, ferric 1-hydroxyethylidene-1,1-diphosphate, ferrous 1-hydroxyethylidene-1,1-diphosphate, ferrous ethylenediaminetetraacetate, ferric diethylenetriaminepentaacetate, ferrous diethylenetriaminepentaacetate, ferric citrate, ferrous citrate, ferric ethylenediaminetetramethylenephosphate, ferrous ethylenediaminetetramethylenephosphate, ferric nitrilotrimethylenephosphate and ferrous nitrilotrimethylenephosphate.
• inorganic iron salts such as ferric chloride, ferrous chloride, ferric phosphate, ferric bromide, ferric nitrate and ferrous n
• organic acid salts may be in the form of free acids, or of sodium salts, potassium salts, ammonium salts, lithium salts, or alkylammonium salts such as a triethanol ammonium salt, a trimethyl ammonium salt and a tetramethyl ammonium salt.
• These soluble salts may preferably be used in a concentration of at least 5 x 10 ⁇ 3 mol/lit., preferably in the range of 8 x 10 ⁇ 3 mol/lit. to 150 x 10 ⁇ 3 mol/lit., and more preferably in the range of 12 x 10 ⁇ 3 mol/lit. to 100 x 10 ⁇ 3 mol/lit., in the stabilizing solution.
• These soluble salts may be added to the stabilizing solution (tank solution) by adding any of them to a stabilizing solution replenisher. Alternatively, they may be added to the stabilizing solution (tank solution) by causing any of them to dissolve out from a light-sensitive material to the stabilizing solution. Still alternatively they may be added to the stabilizing solution (tank solution) by adhering any of them to a light-sensitive material being processed so that it can be carried in the stabilizing solution from a forebath.
• a stabilizing solution having been made to have 5 pm or less of calcium ions and magnesium ions by an ion-exchange resin treatment may be used.
• a method wherein the mildewproofing previously described and a halogen ion releasing compound are incorporated in such a stabilizing solution may also be used.
• the pH of the stabilizing solution may preferably be in the range of 5.5 to 10.0.
• the pH adjusters that can be contained in the stabilizing solution may be any of commonly known alkali agents and acid agents.
• the stabilizing solution may be replenished in a quantity preferably 0.1 time to 50 times, and particularly preferably 0.5 time to 30 times, the carry-in quantity of a forebath (the bleach-fixing solution) per unit area of a light-sensitive material, in view of rapid processing performance and storage stability of dye images.
• the stabilizing may preferably be carried out using 1 stabilizing tank to 5 stabilizing tanks, more preferably 1 tank to 3 tanks, and most preferably 1 tank in view of desilvering and rapid processing.
• a light-sensitive material that is referable for applying the present invention will be described below.
• Silver halide grains preferably used in the light-sensitive material are silver halide grains mainly composed of silver chloride, containing silver chloride in an amount of at least 80 mol %, preferably not less than 90 mol %, more preferably not less than 95 mol %, and most preferably not less than 99 mol %. This is effective for rapid processing and also for stain prevention. It is a preferred embodiment of the present invention to process a light-sensitive material making use of such a silver halide emulsion mainly composed of silver chloride.
• the above silver halide emulsion mainly composed of silver chloride may contain, in addition to silver chloride, other silver halide comprised of silver bromide and/or silver iodide.
• silver bromide may preferably be in an amount of not more than 20 mol %, more preferably not more than 10 mol %, and still more preferably not more than 3 mol %.
• the silver iodide may preferably be in an amount of not more than 1 mol %, more preferably 0.5 mol %, and most preferably 0 mol %.
• Such silver halide grains mainly composed of silver chloride, containing 80 mol % or more of silver chloride, may be applied to at least one silver halide emulsion layer. They may more preferably be applied to all silver halide emulsion layers.
• the crystals of the silver halide grains described above may be regular crystals or twinned crystals, or may be of any other form. Those having any ratio of [1.0.0] face to [1.1.1] face can be used.
• these silver halide grains may have a structure which is uniform from the interior to the outer surface, or a layer structure wherein the inside and the outer surface are of different nature (i.e., a core/shell type).
• These silver halide grains may be of the type wherein a latent image is mainly formed on the surface, or the type wherein it is formed in the interior of grains.
• Tabular silver halide grains see Japanese Patent O.P.I. Publication No. 113934/1983 and Japanese Patent O.P.I. Publication No. 47959/1986) can also be used. It is also possible to use the silver halide grains as disclosed in Japanese Patent O.P.I. Publications No. 26837/1989, No. 26838/1989 and No. 77047/1989.
• the above silver halide grains may be those obtained by any preparation method such as the acid method, the neutral method or the ammonia method.
• They may also be those prepared by a method in which seed grains are formed by the acid method, which are then made to grow by the ammonia method capable of achieving a higher grow rate until they come to have a given size.
• the silver halide emulsion layer of the light-sensitive material processed by the method of the present invention has color couplers. These color couplers react with oxidized products of color developing agents to form non-diffusible dyes.
• the color couplers may advantageously be combined in a non-diffusible form in a light-sensitive layer or in contiguity thereto.
• a red-sensitive layer can contain, for example, a non-diffusible color coupler capable of producing a cyan-part color image, usually a phenol or ⁇ -naphthol coupler.
• a green-sensitive layer can contain, for example, at least one non-diffusible color coupler capable of producing a magenta-part color image, usually a 5-pyrazolone or pyrazolotriazole coupler.
• a blue-sensitive layer can contain, for example, at least one non-diffusible color coupler capable of producing a yellow-part color image, usually a color coupler having an open chain ketomethylene group.
• the color couplers can be, for example, six-, four- or two-equivalent couplers.
• two-equivalent couplers are particularly preferred.
• Suitable couplers are disclosed, for example, in the following publications: Mitanderen aus den Anlagenslaboratorien der Agfa; W. Pelz, "Farbkuppler” in Leverkusen/München, Vol. III, p.111 (1961); The Chemistry of Synthetic Dyes, Vol. 4, pp.341-387, Academic Press; and The Theory of the Photographic Process, Fourth Edition, pp.353-362; and Research Disclosure No. 17643, Section VII.
• magenta coupler represented by Formula M-1 as described on page 29 of Japanese Patent O.P.I. Publication No. 106655/1985 (including as specific exemplary magenta couplers, the compounds No. 1 to No. 77 described on pages 26 to 34 of Japanese Patent O.P.I. Publication No.
• the cyan couplers represented by the formula C-I or C-II also described on pages 34 including as specific exemplary cyan couplers, the compounds C′-1 to C′-82 and C ⁇ -1 to C ⁇ -36 described on pages 37 to 42 of the same publication
• the high-speed yellow couplers also described on page 20 including as specific exemplary yellow couplers, the compounds Y′-1 to Y′-39 described on pages 21 to 26 of the same publication.
• Such a nitrogen-containing heterocyclic mercapto compound can be exemplified by the compounds I′-1 to I′-87 described on pages 42 to 45 of the above Japanese Patent O.P.I. Publication No. 106655/1988.
• the silver halide emulsion mainly composed of silver chloride, containing 80 mol % or more of silver chloride can be prepared by any conventional methods, for example, the single-jet or double-jet method wherein materials are constantly or acceleratingly fed. It may preferably be prepared by the double-jet method under control of the pAg, see Research Disclosure No. 17643, Sections I and II.
• the emulsion mainly composed of silver chloride can be chemically sensitized.
• Sulfur-containing compounds such as allylisothicyanate, allylthiourea and thiosulfate are particularly preferred therefor.
• Reducing agents can also be used as chemical sensitizers, which are exemplified by the silver compounds as disclosed in Belgian Patents No. 493,464 and No. 568,687, the polyamines such as diethylenetriamine, or aminomethylsulfine derivatives, as disclosed in Belgian Patent No. 547,323.
• Noble metals such as gold, platinum, palladium, iridium, ruthenium and rhodium and their noble metal compounds are also suitable sensitizers.
• the emulsion mainly composed of silver chloride can be optically sensitized by known methods using, for example, commonly available polymethine dyes such as neutrocyanine, rhodacyanine and hemicyanine, styryl dyes, oxonols and their analogues, see F.M. Hamer, "The Cyanine Dyes and Related Compounds” (1964), Ullmanns Enzyklpadie der Technischen Chemie, Fourth Edition, Vol. 18, p.431 and the next page, and the above Research Disclosure No. 17643, Section IV.
• polymethine dyes such as neutrocyanine, rhodacyanine and hemicyanine, styryl dyes, oxonols and their analogues
• antifoggants and stabilizers can be used, which are conventionally used.
• Azaindenes are particularly suitable stabilizers, and tetraazaindene and pentaazaindene are preferred. In particular, those substituted with a hydroxyl group or an amino group are preferred.
• the compounds of this type are disclosed, for example, in a Birr's paper, Zeitschrift fürmaschinerich Photographie (Z. Wiss. Photo.), 47 , pp.2-58 (1952) and the above Research Disclosure No. 17643, Section IV.
• the components of the light-sensitive material can be incorporated by conventionally known methods, see, for example, U.S. Patents No. 2,322,027, No. 2,533,514, No. 3,689,271, No. 3,764,336 and No. 3,765,897.
• the components of the light-sensitive material as exemplified by couplers and UV absorbents, can also be incorporated in the form of latex, see German Patent Application Publication No. 2,541,274 and European Patent Application No. 14,921.
• the components can also be fixed in the light-sensitive material in the form of polymers, see, for example, German Patent Application Publication No. 2,044,992, and U.S. Patents No. 3,370,952 and No. 4,080,211.
• supports for the light-sensitive material usual supports can be used, which are exemplified by a support made of a cellulose ester such as cellulose acetate, and a support made of polyester.
• a support made of a cellulose ester such as cellulose acetate
• polyester a support made of polyester
• reflection-type supports such as a support made of paper.
• These may be coated, for example, with a polyolefin, in particular, polyethylene or polypropylene.
• a polyolefin in particular, polyethylene or polypropylene.
• the light-sensitive material for which the color developing solution of the present invention is used may be a light-sensitive material processed by what is called the coupler-in-emulsion type developing method, containing couplers in the light-sensitive material.
• the present invention can be applied to any light-sensitive materials of such a type, such as color papers, color negative films, color positive films, slide color reversal films, motion picture color reversal films, TV color reversal films and reversal color papers.
• the present invention is most preferably applied to color papers mainly composed of silver chloride.
• each layer with the constitution shown below was provided by coating, to produce a multi-layer light-sensitive silver halide color photographic material.
• Coating solutions were prepared in the following way:
• This dispersion was mixed with a blue-sensitive silver halide emulsion (containing 10 g of silver) prepared under the conditions described later to give a first layer coating solution.
• Second layer to seventh layer coating solutions were also prepared in the same procedure as the first layer coating solution.
• H-1 The following H-1 was used as a hardening agent.
• the pAg was controlled by the method disclosed in Japanese Patent O.P.I. Publication No. 45437/1984 and the pH was controlled using an aqueous solution of sulfuric acid or sodium hydroxide.
• the emulsion was desalted using an aqueous 5 % solution of Demol-N, produced by Kao Atlas Co and an aqueous 20 % solution of magnesium sulfate, and then mixed with an aqueous gelatin solution to give a monodisperse cubic emulsion EMP-1 having an average grain size of 0.85 ⁇ m, a variation coefficient ( ⁇ /r) of 0.07 and a silver chloride content of 99.5 mol %.
• EMP-1 blue-sensitive silver halide emulsion
• EMP-1 The same procedure for the preparation of EMP-1 was repeated except that the addition time of the solutions A and B and the addition time of the solutions C and D were changed, to give a monodisperse cubic emulsion EMP-2 having an average grain size of 0.43 ⁇ m, a variation coefficient ( ⁇ /r) of 0.08 and a silver chloride content of 99.5 mol %.
• the emulsion EMP-2 was subjected to chemical sensitization at 55°C for 120 minutes using the following compounds to give a green-sensitive silver halide emulsion (EmB).
• EMP-1 The same procedure for the preparation of EMP-1 was repeated except that the addition time of the solutions A and B and the addition time of the solutions C and D were changed, to give a monodisperse cubic emulsion EMP-3 having an average grain size of 0.50 ⁇ m, a variation coefficient ( ⁇ /r) of 0.08 and a silver chloride content of 99.5 mol %.
• the emulsion EMP-3 was subjected to chemical sensitization at 60°C for 90 minutes using the following compounds to give a red-sensitive silver halide emulsion (EmC).
• the sample thus obtained was exposed to light by a conventional method, and then processed under the following conditions and using the following processing solutions.
• the amount of replenishment is an amount per 1 m2 of the light-sensitive material.
• the stabilizing tanks were arranged in a third to first countercurrent system to carry out replenishment.
• the running processing was carried out in the following way: Tanks of an automatic processor were filled with the above color developing tank solution and also with the above bleach-fixing tank solution and stabilizing tank solution. While the above color paper sample was processed, the above color developing replenishing solution, bleach-fixing replenishing solution and stabilizing replenishing solution were supplied at intervals of 3 minutes through metering pumps.
• the running processing was intermittently carried out at 0.05 R per day until the amount of the color developing replenishing solution supplied in the color developing tank solution reached 3 times the capacity of the color developing tank.
• 1R means that the color developing replenishing solution is supplied in the amount corresponding to the capacity of the color developing tank.
• Color-forming performances, fog and gradation in the above running processing were measured on their values at the start of running processing and at the time of its completion, and values of variations on the values at the time of completion with respect to the values at the start were determined.
• tan ⁇ ⁇ (minimum reflection density + 0.5) - (minimum reflection density + 0.1) ⁇ /(logE1 - logE2)
• the buffering agents used for comparison are as shown in the following. When two kinds of buffering agents were used in combination, they were added in equimolar amounts for each.
• the combination according to the present invention has made it possible to provide a processing method that is superior in color-forming performance or fog, and causes less variations in color-forming performance, fog and gradation, that are due to the influences of the components dissolved out form the light-sensitive material which accumulate as a result of low-replenishing running processing.
• Running processing was carried out under the same conditions as in the processing No. 1-8 of Example 1 except that the chelating agent, diethylenetriaminepentaacetic acid used in the color developing tank solution and color developing replenishing solution was replaced with those as shown in Table 2 and the color developing replenishing solution was supplied in an amount of 30 ml/m2. Color-forming performance, fog and gradation were similarly evaluated to obtain the results shown in Table 2.
• the brightening agents were each added in an amount of 2.0 g/lit in the color developing tank solution and 4.0 g/lit. in the color developing replenishing solution.
• the present invention can improve the stability of photographic performances when light-sensitive silver halide color photographic materials are processed by the low-replenishing method, in particular, when they are intermittently processed in a small processing quantity. Stated specifically, it can provide a method of processing a light-sensitive silver halide color photographic material, that can obtain a stable color-forming performance, i.e., maximum density, can give less fog density and also may cause less variations of gradation.

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