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

• This invention relates to a method of processing a silver halide color photographic light sensitive material and particularly to silver halide color photographic light sensitive materials which can rapidly be processed even in a series of continuous processes without producing any stain in the unexposed areas of the light sensitive materials and can display an excellent processing stability.
• a desilvering step for desilvering a produced metal silver and then a washing or stabilizing step are to be carried out after completing a color developing step.
• Process RA-4 proposes a technique of rapidly processing color papers, that is so-called Process RA-4 comprising three processing steps, namely, a 45-second color developing step, a 45-second fixing and bleaching step and a 90-second stabilizing step so as to process a color paper within 3 minutes at a processing temperature of 35°C.
• the techniques falling within the above classification (1) include, for example, (i) the techniques each by which a silver halide composition is improved, (e.g., a technique of making a silver halide finely grained, such as disclosed in Japanese Patent Publication Open to Public Inspection - hereinafter abbreviated to as JP OPI Publication- No. 51-77223/1976 and the other techniques each of making a silver halide to have a low silver iodide content, such as disclosed in JP OPI Publication No. 58-18142/1983 and JP Examined Publication No.
• the techniques falling within the above classification (2) include, for example, the techniques each for stirring a processing solution, (e.g., the techniques each for stirring a processing solution, such as disclosed in JP OPI Publication No. 62-180369/1987).
• the techniques falling within the above classification (3) include, for example, the known techniques such as (i) a technique in which a development accelerator is used; (ii) another technique for making a concentration of a color developing agent higher; and (iii) a further technique for making a concentration of halide ions including particularly bromide ions lower.
• the following techniques can display particularly excellent rapid processing functions; namely, the techniques such as those disclosed in JP OPI Publication Nos. 58-95345/1983, 60-19140/1985 and 58-95736/1983 each in which a light sensitive material having a high silver chloride content is used, that is retated to the above-mentioned techniques of classification (1).
• an object of the invention to provide a method of processing a silver halide color photographic light sensitive material wherein a rapid processing can be performed even in a series of continuous processing operations, a stain can be prevented from producing in every unexposed are, an excellent processing stability can be displayed and a long-term continuous processing can be performed.
• the above-mentioned object can further effectively be achieved when the above-mentioned silver halide color photographic light sensitive material contains a silver coating weight of not more than 0.75 g/m 2 or a compound represented by the following Formula (2).
• R 1 and R 2 represent each a hydrogen atom, an alkyl group, an aryl group, in which R' represents an alkoxy group, an alkyl group or an aryl group or R 1 and R 2 may combine to form a ring, provided that R 1 and R 2 are not a hydrogen atom simultaneously.
• the problems can be improved by processing the light sensitive material with a processing solution containing a color developing agent in an amount of not less than 1.0x10- 2 mols per liter, however, on the other hand, the other new problems are raised, that is, a problem that the color developing agent is substantially low in solubility so that it can hardly be dissolved unless it is heated upto a high temperature or it is deposited at a low temperature, and another problem that the developing agent is deposited in the course of trying a running experiment.
• the present inventors have discovered that the solubility and deposition of the color developing agent can be improved so that the stable characteristics can be displayed, when making a compound represented by Formula (1) present in a processing solution so as to solve the problems, and the inventors have achieved the objects of the invention. It was also unexpectedly proved to be effective for improving the tar production in the color developer.
• processing steps may be included in the preferable processing steps carried out in the method in which a processing solution of the invention is applied;
• the steps (1), (2) and (3) are preferably applied.
• the color developing solutions applicable to the invention are each to contain a compound represented by Formula (1).
• the alkyl groups having 1 to 8 carbon atoms which are represented by R, include for example, a methyl group, a carboxymethyl group, a phenylmethyl group, an ethyl group, a hydroxyethyl group, a sulfonylethyl group, a propyl group, a butyl group, a heptyl group and an octyl group. These groups may be straight-chained or branched and may also include those each having a substituent.
• Such substituents include, for example, a halogen atom (such as a chlorine atom and a bromine atom), an aryl group (such as a phenyl group), a hydroxyl group, an amino group, a nitro group, a carboxylic acid group (including the salts thereof) and a sulfonic acid group (including the salts thereof).
• a halogen atom such as a chlorine atom and a bromine atom
• an aryl group such as a phenyl group
• a hydroxyl group such as an amino group, a nitro group, a carboxylic acid group (including the salts thereof) and a sulfonic acid group (including the salts thereof).
• the phenyl groups represented by R include those each having a substituent.
• substituents include, for example, a halogen atom (such as a chlorine atom and a bromine atom), an alkyl group (including, preferably, an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group and a butyl group), a hydroxyl group, an amino group, a nitro group, a carboxylic acid group (including the salts thereof) and a sulfonic acid group (including the salts thereof).
• the substituents on the phenyl groups may be a single substituent or 2 to 5 substituents. In the case of 2 to 5 substituents, these substituents may be the same as or the different from each other.
• R may represent an ethylenically-unsaturated group or a polymer having the repetition unit of these ethylenically-unsaturated groups.
• R represents, desirably, a phenyl group and, preferably, a phenyl group having a substituent.
• the preferable substituents thereto include, for example, an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, a carboxylic acid group (including the salts thereof) and a sulfinic acid group (including the salts thereof).
• each of the compounds having a sulfonic acid group or a carboxylic acid group includes, as the matter of course, the compounds such as the sodium salts, potassium salts and lithium salts of the respective compounds, because they are to be used in a color developer that is an alkaline solution.
• the sulfonic acid derivatives of the invention may be used independently or in combination. They may be used in an amount within the range of, desirably, 5.0 g to 100 g and, preferably, 10 g to 80 g per liter of a color developer to be used.
• the effects of the invention can hardly be displayed when making use of the sulfonic acid derivatives represented by Formula (1) in an amount not more than 5.0 g per liter of a color developer to be used and, when making use thereof in an amount not less than 10 g/liter and, preferably, not less than 20 g/liter, a color developing agent contained in a color developing replenisher and a color developer can be so remarkably maintained as to be a high concentration, so that the characteristics of a subject light sensitive material can be stabilized and, in particular, the effects of the invention can also remarkably be displayed in a color developer having a substantially high chloride concentration.
• a color developing solutions appl icable to a developing step include, preferably, an alkaline solution principally comprising an aromatic primary amine type color developing agent.
• an aromatic primary amine type color developing agent preferably, a paraphenylenediamine type compound is preferably used.
• the examples thereof include, typically, 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-((3-hydroxyethyl)aniline, 3-methyl-4-amino-N-ethyl-N-((3-methanesulfonamidoethyl)aniline, 3-methyl-4-amino-N-ethyl-N-((3-methoxyethyl) aniline and the sulfates, hydrochlorides, phosphates or p-toluenesulfonates thereof.
• the salts thereof are generally stable more than the diamines themselves.
• a p-toluenesulfonate is rather useful from the viewpoint of making a color developing agent highly concentrated.
• the following compounds may preferably be used;
• the color developing agents may be commonly used in an amount within the range of 1 ⁇ 10 -2 to 2x10- 2 mol per liter of a color developer to be used.
• the color developing agents may be used in an amount within the range of 1.5x10- 2 to 2.0x1 0-1 mol/liter and, preferably, 2.0x10- 2 to 1.0x1 0-1 mol/liter.
• the preservatives applicable to a color developing solutions include, for example, a sulfite.
• sulfites include, for example, sodium sulfite, sodium hydrogensulfite, potassium sulfite and potassium hydrogensulfite.
• the sulfites may be used in an amount of not more than 1.0x10- 2 mol/liter, desirably not more than 5.0 ⁇ 10 -3 mol/liter and, preferably 0 from the viewpoint of a rapidity.
• the other preservatives than the above-mentioned sulfites include, for example, an organic preservatives such as hydroxylamine, the hydroxylamine derivatives disclosed in JP OPI Publication Nos.
• the effects of the invention including, particularly, the staining prevention effect can excellently be displayed when making use of a compound represented by the following Formula 2 or B and a dialkyl hydrazine in a color developing solution.
• R 1 and R 2 represent each a hydrogen atom, an alkyl group, an aryl group or in which R' represents an alkoxy group, an alkyl group or an aryl group; provided, R 1 and R 2 shall not represent hydrogen atoms at the same time and both of R 1 and R 2 may form a ring.
• R 1 and R 2 represent each an alkyl group, an aryl group, or a hydrogen atom, provided, both of R 1 and R 2 shall not represent hydrogen atoms at the same time.
• the alkyl groups represented respectively by R 1 and R 2 may be the same with or the different from each other and, among the alkyl groups, those having 1 to 3 carbon atoms are preferred.
• R' represents an alkoxy group, an alkyl group or an aryl group.
• the alkyl groups and the aryl groups each represented by R 1 , R 2 and R' include those having a substituent.
• R 1 and R 2 are allowed to couple to each other so as to form a ring including, for example, a heterocyclic ring such as those of piperidine, pyridine, triazine or morpholine.
• R 11 , R 12 and R 13 represent each a hydrogen atom, a substituted or non-substituted alkyl, aryl or heterocyclic group and R 14 represents a hydroxy group, a hydroxyamino group or a substituted or unsubstituted alkyl, aryl, heterocyclic, alkoxy, aryloxy, carbamoyl or amino group.
• the heterocyclic group has a 5 or 6 membered ring and is comprised of each of C, H, O, N and S atoms and a halogen atom, and they may be saturated or unsaturated;
• R 14 represents a group selected from the group consisting of an alkyl group, an aryl group and a heterocyclic group, and R 13 and R 14 are allowed to form a heterocyclic ring in association with each other.
• hydroxylamine type compounds represented by the foregoing Formula 2 are given in U.S. Patent Nos. 3,287,125, 3,293,034 and 3,287,124.
• the particularly preferable compounds thereof include, for example, diethyl hydroxylamine, N-hydroxymorpholine and dimethoxyethyl hydroxylamine each typically exemplified in JP Application No. 2-172374/1990, pp.51-53.
• R 11 , R 12 and R 13 represent each desirably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms and R 11 and R 12 preferably represent each a hydrogen atom.
• R 14 represents desirably an alkyl, aryl, carbamoyl or amino group and particularly an alkyl or a substituted alkyl group.
• the preferable substituents for the alkyl groups include, for example, a carboxyl group, a sulfo group, a nitro group, an amino group and a phosphono group.
• the typical examples of the compounds represented by Formula B include the compounds given in JP Application No. 2-172374/1990, pp.55-59.
• the compounds represented by Formula 2 or B are commonly used in the forms of a free amine, a hydrochloride, a sulfate, a p-toluenesulfonate, an oxalate, a phosphate or an acetate.
• the compounds represented by Formula 2 or B are to have a concentration within the range of commonly 0.4 to 100 g/liter, preferably 1.0 to 60 g/liter and more preferably 2 to 30 g/liter.
• the compounds represented by Formula 2 or B may be used together with any conventional hydroxylamines and a variety of organic preservatives in combination. It is, however, preferred not to use any hydroxylamine, from the viewpoint of the developability.
• the compounds represented by Formula 2 or B may be used independently or in combination.
• triazinyl stilbene type fluorescent whitening agent in the color developing solutions of the invention.
• these triazinyl stilbene type fluorescent whitening agent those given in JP Application No. 2-172374/1990, pp.65-67, in particular, may preferably be used.
• the triazinyl stilbene type fluorescent whitening agent preferably applicable to the invention can be synthesized in an ordinary process such as the process described in, for example, The Chemical Products Industry Association, 'Fluorescent Whitening Agents', issued in Aug. 1976, p.8.
• the triazinyl stilbene type fluorescent whitening agent may be used in an amount within the range of, preferably, 2 to 10 g/liter of a color developing solution to be used and, more preferably, 0.4 to 5 g/liter thereof.
• methyl cellosolve methyl cellosolve, methanol, acetone, dimethyl formamide, (3-cyclodextrin and, the compounds described in JP Examined Publication Nos. 47-33378/1972 and 44-9509/1969, if required, so as to serve as an organic solvent for increasing the solubility of a developing agent to be used.
• auxiliary developing agents include, for example, an N-methyl-p-aminophenol sulfate, phenidone, N,N-diethyl-p-aminophenol hydrochloride and an N,N,N',N'-tetramethyl-p-phenylenediamine hydrochloride.
• These auxiliary developing agents may be added in an amount within the range of, commonly, 0.01 to 1.0 g/liter.
• additives such as a staining inhibitor, a sludging inhibitor and an interlayer effect accelerator.
• a color developing solution is to have a concentration of chlorides (such as potassium chloride, sodium chloride and ammonium chloride) is to be not less than 4xl 0- 2 mol/liter and preferably within the range of 6.0x10- 2 mol/liter to 3.0x10-' mol/liter of the color developing solution.
• chlorides such as potassium chloride, sodium chloride and ammonium chloride
• concentration thereof is less than 4.0x10- 2 mol/liter, the effects of the invention can hardly be displayed satisfactorily and, when exceeding 3.0x10- 1 mol/liter, the concentration is libely to be lowered even if making a color developing agent highly concentrated.
• the suspending agents applicable to the invention include, for example, a variety of metal chelate-forming compounds such as an aminopolycarboxylic acid, e.g., ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid and cyclohexanediaminetetraacetic acid; an aminopolyphosphonic acid, e.g., ethylenediaminetetramethylenephosphonic acid and nitrilotrimethylenephos- phonic acid; and an alkylidenediphosphonic acid typified by 1-hydroxyethylidene-1,1-diphosfonic acid.
• an aminopolycarboxylic acid e.g., ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid and cyclohexanediaminetetraacetic acid
• an aminopolyphosphonic acid e.g., ethylenediaminet
• the above-given chelating agents may be added in an amount within the range of 0.1 to 20 g/literof a color developing solution to be used and preferably 0.2 to 8 g/liter thereof.
• the color developing solutions of the invention are to contain each of anionic, cationic, amphoteric and nonionic surfactants therein and, in particular, the compounds represented by Formula I given in JP Application No. 2-38072/1990 are useful for enhancing the effects of the invention.
• the above-mentioned color developing solutions may be used within any desired range of pH values. However, from the viewpoint of a rapid processing efficiency, they may be used at a pH within the range of, preferably, pH9.5 to 13.0 and, more preferably, pH9.8 to 12.0. They may also be used at a processing temperature of not lower than 36.0°C, preferably, within the range of 38.0 to 43.0°C, and more preferably, 38.5 to 41°C. They may further be used for a processing time of not longer than 90 seconds and within the range of, preferably, not shorter than 3 seconds to not longer than 45 seconds and, more preferably, not shorter than 5 seconds to not longer than 35 seconds.
• an organic inhibitor such as a nitrogen-containing heterocyclic compound, a mercapto group-containing compound, an aromatic compound, an onium compound and a compound having an iodine atom in the substituent thereof.
• the color developing solutions relating to the invention may be replenished in an amount of, ordinarily, not more than 160 ml per m 2 of a light sensitive material to be processed and within the range of, preferably, 20 ml to 120 ml, more desirably, 30 ml to 100 ml and, more preferably, 35 ml to 90 ml
• the ferric organic acid complex salts represented by the following Formula C or D may preferably be used for embodying the invention.
• a 1 through A4 may be the same as or the different from each other and represent each -CH 2 OH, -COOM or -P03M1M2 in which M, M 1 and M 2 represent each a hydrogen atom, an alkali metal or ammonium; and
• X represents a substituted or unsubstituted alkylene group having 3 to 6 carbon atoms.
• a 1 through A4 are each synonymous with those defined in the above-given Formula C; n is an integer of 1 to 8; and B 1 and B 2 may be the same as or the different from each other and represent each a substituted or unsubstituted alkylene group having 2 to 5 carbon atoms.
• ferric organic acid complex salts represented by Formula C or D are detailed in JP OPI Publication Nos. 1-206340/10989 and 1-206342/1989 and JP Application Nos. 2-240400/1990 and 2-240401/1990.
• complex salts ferric 3-diaminopropane tetraacetate complex and ferric glycoletherdiamine tetraacetate complex may particularly be preferable.
• the invention is also allowed to make a combination use of the complex salts of iron (III) aminopolycarboxylic acid such as ethylenediamine tetraacetic acid, diethylenetriamine pentaacetic acid, cyclohexanediamine tetraacetic acid and methylimino diacetic acid, besides the above-mentioned ferric organic acid complex salts.
• complex salts may be used in various combinations as detailed in Research Disclosure No. 24023, April, 1984.
• a bleaching solution substantially comprising of only the ferric complex salts of the compounds represented by the foregoing Formula C or D.
• the expression, 'substantially', herein means that these ferric complex salts are contained in a proportion of at least not less than 70% (in terms of mols) in the whole ferric complex salts. This proportion is to be, preferably, not less than 80%, more preferably, not less than 90% and, preferably, not less than 95%.
• the ferric complex salts of the compounds represented by the foregoing Formula C or D are to be used in an amount of at least 0.10 mol per liter of a bleaching solution to be used and within the range of, desirably, 0.15 mol to 0.6 mol and, preferably, 0.18 mol to 0.5 mol.
• they are to be used in a bleach-fixing solution, they are to be used in an amount within the range of 0.03 mol to 0.3 mol per liter of the bleach-fixing solution to be used and, preferably, 0.05 mol to 0.25 mol per liter.
• the processing solutions having a bleaching function which are relative to the invention, are allowed to contain the compounds represented by Formulas I through IX given in JP Application No. 2-41549/1990, imidazole and the derivatives thereof.
• a bleaching acceleration effect but also a silver-sludge improvement can be displayed besides the above-mentioned effects.
• the above-mentioned bleaching accelerators may be used independently or in combination. They can display the excellent effects as described above, when they are generally added in an amount within the range of about 0.01 to 100 g per liter of a bleaching solution to be used. However, when the amount thereof added is too small, the bleaching acceleration effect is not so much displayed and when it is unnecessarily too much, a precipitation is produced sometimes to stain a silver halide color photographic light sensitive material to be processed. It is, therefore, recommendable to add then in an amount within the range of, preferably, 0.05 to 50 g per liter of a processing solution having a bleaching function to be used and, more preferably, 0.05 to 15 g/liter.
• a bleaching accelerator In the case of adding a bleaching accelerator, it may be added to be solved as it is. However, it is general to add it upon dissolving it in advance in water, an alkaline solution or an organic acid. If required, it is also allowed to add it upon dissolving it with an organic solvent such as methanol, ethanol and acetone.
• the above-mentioned bleaching solution are used at a pH within the range of, desirably, pH2.0 to 5.5 and, preferably, not lower than pH3.0 to not higher than pH5.0.
• pH of a bleaching solution is not lower than 5.5, there may be some instances where a bleach-fog may not satisfactorily be prevented or when the pH thereof is not higher than 2, the photographic characteristics may sometimes be affected, though the bleach-fog may be prevented.
• the processing temperature is to be kept within the range of, preferably, 20°C to 50°C and, more preferably, 25°C to 45°C.
• bleaching solutions are usually used upon adding a halide such as ammonium bromide.
• a halide such as ammonium bromide.
• These bleaching solutions are also allowed to contain pH-buffers comprising a variety of salts including, for example, boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate and ammonium hydroxide, independently or in combination.
• a variety of fluorescent whitening agents, defoamers, surfactants or antimolds may also be contained therein.
• an ammonium ion content is to be not more than 50 mol% of the whole cation, preferably, not more than 20 mol% thereof and, more preferably, not more than 10 mol% thereof.
• any bleach-fog can be prevented.
• the above-mentioned bleaching solutions may be replenished in an amount within the range of, 20 ml to 400 ml per m 2 of a silver halide color photographic light sensitive material to be processed, preferably, 30 ml to 350 ml, more preferably, 40 ml to 300 ml and, most preferably, 50 ml to 250 ml.
• a subject light sensitive material is to be processed with a bleaching solution and successively processed with a fixing solution or a bleach-fixing solution.
• the fixing agents include, for example, a compound capable of forming the complex salts of an aqueous solution upon making a reaction with a silver halide.
• a compound capable of forming the complex salts of an aqueous solution upon making a reaction with a silver halide include, for example, a thiosulfate such as potassium thiosulfate, sodium thiosulfate and ammonium thiosulfate; a thiocyanate such as potassium thiocyanate, sodium thiocyanate and ammonium thiocyanate; thiourea; and thioether.
• a thiosulfate and a thiocyanate are preferably used and a thiocyanate is more preferably used.
• ammonium ions in a fixing solution or a bleach-fixing solution in an amount of not more than 50 mol% of the whole cation as in the aforementioned bleaching solution and, preferably, not more than 20 mol%.
• a stain-prevention effect may be displayed though the effects may be displayed a little.
• the fixing solutions and the bleach-fixing solutions are also allowed to contain, besides the above-mentioned fixing agents, pH buffers comprising a variety of the salts including, for example, sulfites such as ammonium sulfite, potassium sulfite, ammonium bisulfite, potassium by sulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite and sodium metabisulfite, and various salts of boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate and ammonium hydroxide, independently or in combination.
• sulfites such as ammonium sulfite, potassium sulfite, ammonium bisulfite, potassium by sulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite and sodium metabisulfite
• boric acid borax
• an alkali halide or an ammonium halide including, for example, a re-halogenizing agent such as potassium bromide, sodium bromide, sodium chloride and ammonium bromide. It is further allowed to suitably add, for example, a pH buffer such as a borate, an oxalate, an acetate, a carbonate and a phosphate, and the compounds generally known as the additives for fixing solutions and bleach-fixing solutions, such as an alkylamine and a polyethylene oxide.
• a pH buffer such as a borate, an oxalate, an acetate, a carbonate and a phosphate
• the compounds generally known as the additives for fixing solutions and bleach-fixing solutions such as an alkylamine and a polyethylene oxide.
• the above-mentioned fixing agents are to be added in an amount of not less than 0.1 mols per liter of a processing solution to be used and within the range of, desirably, 0.3 mols to 4 mols, more desirably, 0.5 mols to 3.0 mols and, preferably, 0.6 mols to 2.0 mols per liter thereof.
• a processing replenisher reservoir tank or a suitable oxidizer such as hydrogen peroxide, a bromate and a persulfate may further be added so as to enhance the activity of a bleaching solution or a bleach-fixing solution.
• a silver recovery can be carried out of a fixing solution or a bleach-fixing solution in any known methods.
• a fixing solution or a bleach-fixing solution may be replenished in an amount of, not more than 800 ml per m 2 of a subject light sensitive material, preferably, within the range of 20 ml to 650 ml per m 2 thereof and, more preferably, within the range of 30 ml to 400 ml per m 2 thereof. In the latter case, the excellent results can be enjoyed.
• a fixing solution or a bleach-fixing solution contains an iodide (such as ammonium iodide, potassium iodide, sodium iodide and lithium iodide) in an amount within the range of 0.1 g/liter to 10 g/liter, the effects of the invention can be promoted.
• an iodide such as ammonium iodide, potassium iodide, sodium iodide and lithium iodide
• the compounds represented by Formula [FA] or [FB] given in JP Application No. 2-41549/1990 are preferably used in a fixing solution or a bleach-fixing solution, for the purpose of freeing ammonia.
• a sulfite adduct is preferably used in a fixing solution or a bleach-fixing solution.
• Such sulfite adducts preferably applicable thereto include, for example, those having Formulas (A-1) through (A-11) given in JP Application No. 2-41549/1990.
• Such a sulfite adduct is used in an amount within the range of, desirably, 0.1 g to 80 g/liter of a processing solution to be used and, preferably, 0.5 to 40 g/liter thereof.
• the total processing time of a bleaching solution and a processing solution (i.e., a fixing solution or a bleach-fixing solution) having a fixing function is not longer than 3 minutes 45 seconds and within the range of, preferably, 40 seconds to 3 minutes and, more preferably, 60 seconds to 2 minutes 40 seconds.
• Any desired bleaching time may freely be selected out of the above-mentioned range of the total processing time, however, it is to be within the range of, preferably, 10 seconds to 70 seconds and, more preferably, 20 seconds to 55 seconds.
• Any desired processing time of the processing solutions each having a fixing function may freely be selected, however, it is to be preferably not longer than 3 minutes 10 seconds and within the range of, more preferably, 10 seconds to 2 minutes 40 seconds.
• the cross-over time between a color developing solution tank and a bleaching solution tank is to be desirably not longer than 10 seconds and, preferably, not longer than 7 seconds, from the viewpoint of preventing a bleach-fog production.
• the forcibly stirring means include, for example, the following means;
• the stabilizing solutions applicable to the invention can be applied to a stabilizing solution to be used in a stabilizing step that is the final processing step applicable to a silver halide color photographic light sensitive material.
• the stabilizing solutions mentioned above can also be applied to the cases where a silver halide color photographic light sensitive material is processed with a processing solution having a fixing function such as a fixing solution or a bleach-fixing solution and is then stabilized in a stabilizing step without substantially washing it.
• the stabilizing solution may be replenished in an amount, preferably, 1 to 80 times as much as an amount carried therein from the precedent bath in terms of a unit area of a subject color light sensitive material.
• the stabilization processing tank is preferably so constructed that the concentration of the component of the precedent bath (i.e., a bleach-fixing solution or a fixing solution), which are carried into the stabilizing solution bath, is to be not more than 1/100 and is to be within the range of 1/100 to 1/100000 and preferably 1/200 to 1/50000 as dense as the whole concentration of the stabilizing solution in the stabilizing tank, from the viewpoints of maintaining a low pollution and a preservability.
• the above-mentioned stabilizing tank may be comprised of a plurality of tanks and it is preferable for the invention that the plural tanks consist of not less than 2 to not more than 6 tanks.
• the tank system when the tanks consist of not less than 2 tanks, it is particularly preferable to constitute the tank system to be a counter-current system (that is a system in which a solution is supplied to a back-bath so that an overflow can be flowed from the fore-bath.), from the viewpoint of the improvements of low pollution and image preservation.
• a counter-current system that is a system in which a solution is supplied to a back-bath so that an overflow can be flowed from the fore-bath.
• the amounts of a solution to be carried into the following bath may be varied according to the kinds of light sensitive materials, the transport rates and transport systems of an automatic processor used and the systems for squeezing the surfaces of light sensitive materials.
• the amount to be carried thereinto are ordinarily within the range of 50 ml/m 2 to 150 m1 2 .
• the amounts of a solution to be replenished relative to the above-mentioned amounts to be carried in, which may remarkably be able to display the effects of the invention, are to be within the range of 50 ml/m 2 to 4.0 liters/m 2 and, preferably, 100 ml/m 2 to 1500 ml/m2.
• the processing temperature thereof is to be within the range of 15 to 60°C and, preferably, 20 to 45°C.
• the stabilizing solutions applicable to the invention are each preferable to contain a chelating agent represented by the formulas [CH-I] through [CH-III] given in JP Application No. 2-41549/1990.
• the chelating agents preferably applicable to the above-mentioned stabilizing solutions may be used in an amount within the range of, 0.01 to 100 g, preferably, 0.05 to 50 g and, more preferably, 0.1 to 20 g.
• the pH values of the above-mentioned stabilizing solutions are to be within the range of, desirably, pH4.0 to 9.0 and, preferably, pH5.5 to 9.0, for the purpose of improving the image preservability.
• the pH controllers applicable to the stabilizing solutions include any one of the generally known alkalizers and acidifiers.
• the stabilizing solutions may be added with organic acid (such as citric acid, acetic acid, succinic acid, oxalic acid and benzoic acid), pH controllers (such as a phosphate, a borate, a hydrochloride and a sulfate), a surfactant, an antiseptic and metal salts such as those of Bi, Mg, Zn, Ni, AI, Sn, Ti and Zr.
• organic acid such as citric acid, acetic acid, succinic acid, oxalic acid and benzoic acid
• pH controllers such as a phosphate, a borate, a hydrochloride and a sulfate
• a surfactant such as those of Bi, Mg, Zn, Ni, AI, Sn, Ti and Zr.
• an antiseptic and metal salts such as those of Bi, Mg, Zn, Ni, AI, Sn, Ti and Zr.
• These compounds may be added thereinto in any amount, provided, the
• the antimolds preferably applicable to the stabilizing solutions applicable to the invention include, for example, a hydroxy benzoate compound, a phenol type compound, a thiazole type compound, a piridine type compound, a guanidine type compound, a carbamate type compound, a morpholine type compound, a quaternary phosphonium type compound, an ammonium type compounds, a urea type compound, an isooxazole type compound, a propanol amine type compound, a sulfamide type compound, an amino acid type compound and a benztriazole type compound.
• a phenol type compound, a thiazole type compound and a benztriazole type compound may further preferably be used, from the viewpoint of a solution preservability.
• These further preferable compounds include, typically, 1,2-benzisothiazoline-3-one, 2-methyl-4-isothiazo- line-3-one, 2-octyl-4-isothiazoline-3-one, 5-chloro-2-methyl-4-isothiazoline-3-one, sodium 0-phenylphenol and benztriazole.
• the amounts of these antimolds to be added into a stabilizing solution are within the range of, desirably, 0.001 g to 20 g per liter of the stabilizing solution to be used and, preferably, 0.005 g to 10 g per liter thereof.
• the stabilizing solutions may be added in combination with the compounds given in JP Application Nos. 2-234776/1990 and 2-234780/1990, including, for example, formalin, hexamethylene tetramine, a triazine type compound, an N-methylol compound (such as dimethylol urea, trimethylol urea, dimethylol guanidine, N-hydroxymethyl hydroxyethyl amine and trimethylol melamine) and aliphatic aldehyde. It is, however, preferable to make formalin to be substantially zero from the viewpoint of pollution prevention and that is a preferable embodiment from the viewpoint of solution preservability.
• the stabilizing solutions each applicable to the invention contain a surfactant represented by Formulas [I] and [III], triethanol amine and polyvinyl pyrrolidones.
• the above-mentioned surfactants and a water-soluble organic siloxane type compound are to be added in an amount within the range of 0.01 to 20 g per liter of a stabilizing solution to be used. When this is the case, an excellent result can be displayed.
• water-soluble organic siloxane type compounds mean each common water-soluble organic siloxane type compounds such as those given in JP OPI Publication No. 47-18333/1972, JP Examined Publication Nos. 55-51172/1980 and 51-37538/1976, JP OPI Publication No. 49-62128/1974 and U.S. Patent No. 3,545,970, respectively.
• water-soluble organic siloxane type compounds may readily be available from UCC (standing for Union Carbide Corp.) and Shin-Etsu Chemical Industrial Co., Ltd.
• the color light sensitive materials applicable to the invention comprise each silver halide grains principally containing silver chloride in a proportion of at least not less than 80 mol%, preferably, not less than 90 mol%, more preferably, not less than 95 mol% and, most preferably not less than 99 mol%.
• these silver halide emulsions principally comprising the above-mentioned silver halide grains are also allowed to contain silver bromide so as to serve as a composition of the silver halides thereof.
• the silver bromide proportion thereof is to be not more than 20 mol%, preferably not more than 10 mol% and more preferably not more than 3 mol%.
• the proportions thereof is to be preferably not more than 1 mol%, more preferably not more than 0.5 mol% and most preferably zero.
• the above-mentioned silver halide grains principally comprising silver chloride having a proportion of not less than 80 mol% may be applied to at least one of silver halide emulsion layers and, preferably, to all of the silver halide emulsion layers.
• the crystals of the above-mentioned silver halide grains may be any one of regular crystals, twinned crystals and others and, therefore, the crystals having any crystal ratios of [1,0,0] faces to [1,1,1] faces may be used.
• the crystal configurations of the above-mentioned silver halide grains may be uniform from the inside to the outside thereof or may be a grain-layer structure having the inside thereof heterogeneous from the outside thereof (i.e., a core-shell type crystal structure).
• these silver halides may be of a type of forming a latent image mainly on the surfaces of the grains or another type of forming a latent image inside the grains.
• tabular-shaped silver halide grains may be used, (For the details, refer to JP OPI Publication No. 58-113934/1983 and JP Application No. 53-170070/1978). Still further, silver halides given in JP OPI Publication Nos. 64-26837/1989, 64-26838/1989 and 64-77047/1989 can be used.lt is further allowed to use the silver halide grains prepared in any one of an acidic method, a neutral method and an ammoniacal method.
• They may also be prepared in a method that seed grains are prepared in an acidic method and are then grown up in an ammoniacal method having a fast grain-growth rate so that the grains are grown up to a specific grain-size.
• seed grains are prepared in an acidic method and are then grown up in an ammoniacal method having a fast grain-growth rate so that the grains are grown up to a specific grain-size.
• the pH and pAg of a reaction chamber are controlled and then silver ions and halide ions are put thereinto in such an amount so as to meet the growth rate of the silver halide grains as disclosed in JP OPI Publication No. 54-48521/1979.
• the silver halide emulsion layers thereof are each to contain color couplers.
• These color couplers produce each a non-diffusible dye upon making reaction with the oxidized products of a color developing agent.
• the color couplers are incorporated into a light sensitive layer or a layer adjacent thereto, in the non-diffusible state.
• a red-light sensitive layer can contain, for example, a non-diffusible color coupler capable of producing the color image of cyan-colored portions and, generally, a phenol or a-naphthol type coupler.
• a green-light sensitive layer can contain, for example, at least one non-diffusible color coupler capable of producing the color image of magenta-colored portions and, generally, a 5-pyrazolone type coupler and pyrazolotriazole.
• a blue-light sensitive layer can contain, for example, at least one non-diffusible color coupler capable of producing the color image of the yellow-colored portions and, generally, a color coupler having an open-chained ketomethylene group.
• Such a color coupler as mentioned above may be any one of 6-, 4- or 2-equivalent couplers.
• 2-equivalent couplers in particular, are preferably used.
• couplers suitably applicable to the invention are disclosed in, for example, the following publications: Nitannonln aus den Anlagenslaboratorien der Agfa, Leverkusen/Munchen, Vol.lll, p.111, 1961, W. Pelz, 'Farbkuppler'; K. Venkataraman, 'The Chemistry of Synthetic Dyes', Vol.4, pp.341-387, Academic Press; 'The Theory of the Photographic Process', 4th Ed., pp.353-362; and Research Disclosure No. 17643, Section VII.
• magenta couplers having the formula [M-1] such as those disclosed in JP OPI Publication No. 63-106655/1988, p.28, among which, the typically exemplified magenta couplers include No.1 through No.77 given in JP OPI Publication No.
• the typical examples of the above-mentioned nitrogen-containing mercapto compounds include, for example, (I'-1) through (1'-87) given in JP OPI Publication No. 63-106655/1988, pp.42-45.
• the above-mentioned silver halide emulsions may be prepared in any ordinary preparation process (including, for example, a single or double influent preparation process in which the materials of the emulsion are flowed in at a constant or accelerating rate.).
• the double influent preparation process is preferable to be carried out with controlling the pAg of the emulsion materials.
• Research Disclosure No. 17643, Sections I and II refer to Research Disclosure No. 17643, Sections I and II.
• Such an emulsion as mentioned above can be chemically sensitized. They may be chemically sensitized with a sulfur-containing compounds including, particularly, an allylisocyanate, an allylthiourea or a thiosulfate.
• a reducing agents can also serve as a chemical sensitizer. These reducing agents include, for example, the silver compounds disclosed in Belgian Patent Nos. 493,464 and 568,687 and the polyamines or aminomethyl- sulfinic acid derivatives, such as diethylene triamine disclosed in Belgian Patent No. 547,323.
• the suitable sensitizers further include, for example, the noble metals such as gold, platinum, palladium, iridium, ruthenium and rhodium and the compounds thereof.
• the emulsions can be optically sensitized in the generally known sensitizing methods in which the ordinary polymethine dyes such as a neutrocyanine, a basic or acidic carbocyanine, a rhodacyanine and a hemicyanine, a styryl dye, an oxonol and the like.
• the ordinary polymethine dyes such as a neutrocyanine, a basic or acidic carbocyanine, a rhodacyanine and a hemicyanine, a styryl dye, an oxonol and the like.
• the ordinary polymethine dyes such as a neutrocyanine, a basic or acidic carbocyanine, a rhodacyanine and a hemicyanine, a styryl dye, an oxonol and the like.
• F.M. Hamer 'The Cyanine Dyes and Related Compounds', 1964, U
• the emulsions may be applied thereto with any commonly usable antifoggants and stabilizers.
• azaindene is a particularly suitable stabilizer and, among them, desirably, tetra- and penta-azaindenes and, preferably, those substituted with a hydroxyl or amino group can be applied thereto.
• This type of the compounds are given in, for example, Birr's treatise disclosed in Z. Wiss. Photo., 47, 1952, pp.2-58 and the above-given Research Disclosure No. 17643, Section IV, respectively.
• the components of a light sensitive material can be contained in the light sensitive material in any commonly known methods.
• the components of a light sensitive material such as a coupler and a UV absorbent may be contained in the form of an electrically charged latex;
• the components thereof can also be fixed in the form of the polymers in the subject light sensitive material;
• German Patent DT-OS No. 2,044,992 and U.S. Patent Nos. 3,370,952 and 4,080,211 for example.
• a silver halide color photographic light sensitive material is to have a silver coating weight of, preferably, not more than 0.75 g per m 2 of the light sensitive material and, more preferably, within the range of 0.2 to 0.7 g per m 2 thereof.
• any ordinary types of supports can be used.
• a reflective support such as a paper support may be used for and they may be coated thereon with a polyolefin including, particularly, polyethylene and polypropylene.
• a polyolefin including, particularly, polyethylene and polypropylene.
• the above-mentioned light sensitive materials may be applied to any kinds of light sensitive materials including, for example, those comprising a color paper, a color negative film, a color positive film, a color reversal slide film, a color reversal cinematographic film, a color reversal TV film and a color reversal paper.
• a multilayered silver halide color photographic light sensitive material (1) was prepared by coating the layers having the following compositions onto a paper support laminated thereon with polyethylene on one side of the paper support and laminated with polyethylene containing titanium oxide on the 1st layer of the other side of the paper support The coating solutions applied thereonto were each prepared in the following manner.
• Yellow coupler (Y-1) of 25.0 g, dye-image stabilizers (ST-1) of 10.0 g and (ST-2) of 6.67 g, and additive (HQ-1) of 0.53 were each added into high boiling organic solvent (DNP) of 6.3 g and ethyl acetate of 60 ml so as to be dissolved together.
• DNP high boiling organic solvent
• the resulting solution was added into an aqueous 10% gelatin solution of 220 ml containing 7 ml of a 20% surfactant (SU-1) solution, and so dispersed as to be emulsified by making use of a supersonic homogenizer, so that a yellow coupler dispersion solution could be prepared.
• the resulting dispersion was mixed with a blue-sensitive silver halide emulsion (containing 10 g of silver) prepared under the following conditions, so that the 1st layer coating solution could be prepared.
• the coating solutions each for the 2nd layer through the 7th layer could be prepared in the same manner as in the 1st layer coating solution.
• (H-1) was added into the 2nd and 4th layers and, (H-2), into the 7th layer, respectively.
• surfactants (SU-2) and (SU-3) were each added so as to control the surface tension of each of the coating solutions.
• the resulting emulsion EMP-1 was subjected to a chemical sensitization by making use of the following compounds by taking 90 minutes, so that blue-sensitive silver halide emulsion (Em-B) could be prepared.
• a monodisperse type cubic emulsion EMP-2 was so prepared as to have an average grain size of 0.43 ⁇ m, a variation coefficient (a/r) of 0.08 and silver chloride content of 99.5% in the same manner as in EMP-1, except that the time for adding solutions (A) and (B) and the time for adding solutions (C) and (D) were changed.
• the resulting EMP-2 was subjected to a chemical sensitization by making use of the following compounds at 55°C by taking 120 minutes, so that green-sensitive silver halide emulsion (Em-G) was prepared.
• a monodisperse type cubic emulsion EMP-3 was so prepared as to have an average grain size of 0.50 ⁇ m, a variation coefficient (a/r) of 0.08 and a silver chloride content of 99.5% in the same manner as in EMP-1, except that the time for adding solutions (A) and (B) and the time for adding solutions (C) and (D) were changed.
• the resulting EMP-3 was subjected to a chemical sensitization by making use of the following compounds at 60°C by takinq 90 minutes, so that red-sensitive silver halide emulsion (Em-R) was prepared.
• the resulting color paper samples had the silver chloride contents of 99.5%.
• Each of the experimental color paper was prepared by changing the above-mentioned silver chloride content as shown in the following Table 4 and they were tested.
• Each of the above prepared color paper was subject to the conventional wedgewise exposure and was processed according to the Processing step (1) as shown in Table 3 below.
• the running treatment was carried out by filling up the above-given color developing tank solution in an automatic processor and, at the same time, a bleaching tank solution, a fixing tank solution and a stabilizing tank solution were filled up therein and then, the above-mentioned color paper samples were each processed while replenishing the above-mentioned color developing replenishing solution, bleaching replenishing solution, fixing replenishing solution and stabilizing replenishing solution each through the metering pumps.
• magenta density i.e., the magenta reflection density
• yellow dye density i.e., the yellow reflection density
• exposed areas i.e., the maximum density areas
• the wedgewise exposed color paper samples were each processed and then the resulting yellow dye densities thereof (i.e., the reflection densities thereof) in the exposed areas (having the maximum density) were measured, so that the density differences from those obtained in the precedent treatment were obtained and evaluated. Further, the behavior of the precipitation (i.e., the crystal deposition) of the solution produced when completing the running treatment and the tar produced in the developing tank were observed upon allowing the developing tank solution completed the running treatment to stand at room temperature for 10 days.
• the light sensitive materials each prepared in Example 1 were subjected to the running process by making use of the color developing solution used in Example 1 and the following processing solutions in accordance with the following processing steps (2).
• the running process was carried out by filling up the above-given processing solutions into an automatic processor and, at the same time, while processing the foregoing color paper samples and replenishing every 3 minutes the above-mentioned color developing replenishing solution, bleach-fixing replenishing solution and stabilizing replenishing solution each through a quantitative pump.
• the running process was carried out by replenishing the color developing replenishing solution into the color developing tank solution until the total amount of the color developing replenishing solution was 3 times as much as the capacity of the color developing tank solution.
• Example 1 The evaluation was made in quite the same manner as in Example 1. The results thereof were proved to be quite the same behavior as in Example 1 and the invention was able to display the effects thereof even when a series of a bleach-fixing step through a stabilizing step were carried out after completing a color developing step.
• Example 9 By making use of the color paper samples prepared in Example 1, the wedgewise exposures were made in the ordinary method and then the running processes were carried out in accordance with the processing steps (1) for Example 1. After that, the experiments and evaluation were made in the same manners as in Example 1. The results thereof are shown in the following Table 9.
• the processing solutions applied to the experiments were the same processing solutions used in Experiment No. 1-13 of Example 1, except that the fluorescent whitening agent (i.e., Compound E-34) was changed to those shown in Table 9.
• Example 5 When each of the same evaluation was made as in Example 5, except that the compound 1-32 of the invention applied to Example 5 was replaced by I-2, I-21, I-20 or 1-37, it was proved that almost the same results of the behavior as in 1-32 could be obtained, but the precipitation and the tar each produced after completing the running process were somewhat deteriorated

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