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
  • G03C7/44—Regeneration; Replenishers
• • 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
  • G03C7/3046—Processing baths not provided for elsewhere, e.g. final or intermediate washings

Definitions

• This invention relates to a process of preparing a silver halide color photographic light sensitive material and, particularly, to a process of preparing a silver halide color photographic light sensitive material, which is capable of performing a stable processing treatments without producing any precipitates but with inhibiting any dyes from being discolored.
• a silver halide color photographic light sensitive material is processed in the following procedures. After exposing it imagewise to light, it is processed in a color developing step and then in a processing step such as a bleaching step and a fixing step or a bleach-fixing step each having a fixing function. Next, it is processed in a stabilizing step and then in a washing step.
• the following compounds are either contained in or adhered to a subject light sensitive material so that the compounds can be brought into the light sensitive material; namely, the compounds capable of producing a water-soluble silver salt upon reaction with a silver halide, such as a thiosulfate or other water-soluble silver complex salts and, further, a sulfite or a metabisulfite as a preservative
• a silver halide such as a thiosulfate or other water-soluble silver complex salts
• a sulfite or a metabisulfite as a preservative
• a stabilizing bath is generally used by containing formaldehyde in the final processing step following after a washing bath.
• Formaldehyde applicable to the above-mentioned stabilizing bath has the effects of keeping the physical properties of a color photographic light sensitive material and, particularly, formaldehyde has the effects of preventing the color photographic light sensitive material from scratching the surface thereof and of preventing a gradation from being deteriorated by gradually hardening the photographic light sensitive material in allowing it to stand.
• formaldehyde has another effect of preventing the stability of a dye image from being deteriorated by an unreacted coupler remaining in the color photographic light sensitive material.
• the regulations include; for example, the laws regulating the specified poisonous substances or violent poisons each stimulating mucous membrane; the regulations for preventing any organic solvent toxicosis or for the articles for house-hold use, each specified in the chemical regulations attached to the OSHA (Occupational Safety and Health Administration Laws); the regulations for fibers and plywoods; and the formaldehyde regulations for underwear and baby-clothes. Accordingly, a technique for reducing formaldehyde application has been long-waited for.
• Processes C-41B and C-41RA which were developed by Eastman Kodak Company with the purpose of making a process more rapid and saving the bath treatments. These processes are each comprised of the steps, namely, (Color developing step) - (Bleaching step) - (Fixing step) - (Stabilizing step) - (Drying step), which are rapid processes without substantially carrying out any washing step.
• the stabilizing solution has to stay longer in the stabilizing tank of an automatic developing machine; a thiosulfate is liable to be decomposed by air-oxidation and so forth; the finely granulated black precipitates of a sulfide are produced; a cotton waste-like suspended matter is produced; a matter is fixed to the tank walls; and tar is produced.
• the techniques for solving the above-mentioned troubles are proposed in, for example, JP OPI Publication No. 2-153348/1990.
• the technique proposed therein is to prevent a subject light sensitive material from being stained in a process in the following manner. After processing the light sensitive material with a processing solution comprising a fixing agent containing a thiosulfate in a proportion within the range of 1.1 to 2.0 mols per liter so as to have a fixing function and, then, when processing the light sensitive material with a stabilizing solution containing at least one of hexamethylene tetramine and the derivatives thereof, hexahydrotriazine and the derivatives thereof and N-methylol compounds, the stains can be prevented from producing.
• the processing method for a silver halide color photographic light sensitive material relating to the invention comprises the steps of processing the silver halide color photographic light sensitive material with a processing solution having a fixing function and then processing the light sensitive material with a stabilizing solution, wherein the stabilizing solution contains a compound selected from the group consisting of the compounds represented by the following Formula [F] and the replenished amount of the stabilizing solution is not more than 670 ml/m2.
• Z represents the group consisting of the atoms necessary to form a substituted or unsubstituted carbon ring or a substituted or unsubstituted heterocyclic ring
• X represents an aldehyde group, wherein R1 and R2 represent each a lower alkyl group
• n is an integer of 1 to 4.
• the present inventors considered that the above-mentioned troubles will become more serious, because the more an automatic processing machine is made compact in size, the more the machine used therein can hardly be maintained.
• the inventors have studied of the technique described in the foregoing JP OPI Publication No. 2-153348/1990. However, it was proved that any complete solution of the problems cannot be expected within the scope of the technique described therein.
• the preferred embodiments include that the substituents for the above-denoted Z are to be an aldehyde group, a hydroxyl group, an alkyl group, an alkoxy group, a halogen atom, a nitro group, a sulfo group, a carboxy group, an amino group, a hydroxyalkyl group, an aryl group, a cyano group, an aryloxy group, an acyloxy group, an acylamino group, a sulfonamido group, a sulfamoyl group, a carbamoyl group or a sulfonyl group.
• Z represents the group consisting of the atoms necessary to form a substituted or unsubstituted carbon ring or a substituted or unsubstituted heterocyclic ring.
• the carbon rings and heterocyclic rings may be either single rings or condensed rings.
• Z represents an aromatic carbon ring having a substituent or a heterocyclic ring. It is also preferable that the substituents for Z are to be the following groups.
• the carbon rings represented by Z include, preferably, a benzene ring and the heterocyclic rings represented thereby include, preferably, a 5- or 6-membered heterocyclic ring.
• the 5-membered rings include, for example, a thiophene, pyrrole, furan, thiazole, imidazole, pyrazole, succinimido, triazole or tetrazole ring.
• the 6-membered rings include, for example, a pyridine, pyrimidine, triazine or thiadiazine ring.
• the condensed rings include, for example, a naphthalene, benzofuran, indole, thionaphthalene, benzimidazole, benzotriazole or quinoline ring.
• Exemplified compounds (F-1) through (F-52) can be prepared by inserting various kinds of substituents shown in the following table into the positions 1 through 6 indicated in the above-given formula.
• the other typically exemplified compounds include the exemplified compounds (76) through (90) given in Japanese Patent Application No. 3-89686/1991, pp.13-14.
• the desirable compounds include, for example, those of (F-2), (F-3), (F-4), (F-6), (F-23), (F-24), (F-52) and (F-61) and the preferable compounds include those of (F-3).
• the compounds represented by Formula [F] can readily be obtained from the commercial products available on the market.
• the compounds represented by Formula [F] are contained in a stabilizing solution applicable to silver halide color photographic light sensitive materials.
• the compounds may also be contained in a processing solution applicable to the preceding bath to a processing bath having a bleaching function, a processing solution having a bleaching function and a processing solution having a fixing function, as well as in a stabilizing solution, provided, the effects of the invention cannot be spoiled.
• the compounds represented by Formula [F] may be added to a stabilizing solution, in an amount within the range of desirably 0.05 to 20 g, more desirably 0.1 to 15 g and preferably 0.5 to 10 g per liter of a stabilizing solution used therein.
• the compounds represented by Formula [F] are characterized in that the image preservability can be more excellent, particularly, even under the low humidity conditions, as compared to the known compounds substitutable for formaldehyde.
• the stabilizing solutions may be replenished in an amount of not more than 670 ml, desirably within the range of not less than 100 ml to not more than 500 ml and, particularly 160 ml to 460 ml per sq,meter of a light sensitive material used.
• the stabilizing solution is replenished in an amount exceeding 670 ml, the waste solution is increased resultingly, so that it may not be desired from the social environmental and economical viewpoints and the effects of the invention may not remarkably be displayed. Therefore, the less a replenishment thereof is so made as not to exceed the limited amount of 100 ml/m2, the more the effects of the invention can be remarkably displayed.
• the pH value of a stabilizing solution is to be not lower than 6.0, desirably not lower than 7.0 and preferably within the range of 7.5 to 9.0.
• the pH controllers which may be contained in a stabilizing solution include also any types of alkalizing agent or an acidifying agent, which are generally known.
• a stabilizing solution contains a chelating agent having a chelating stability constant of not less than 8 to iron ions.
• a chelating stability constant' means a constant well-known from L.G. Sillen ⁇ A.E. Martell, "Stability Constants of Metal-ion Complexes", The Chemical Society, London (1964) and S. Chaberek ⁇ A.E. Martell, "Organic Sequestering Agents", Willey (1959).
• the chelating agents having a chelating stability constant of not less than 8 to iron ions include, for example, an organic carboxylic acid chelating agent, an organic phosphoric acid chelating agent, an inorganic phosphoric acid chelating agent and a polyhydroxy compound.
• the above-mention iron ions mean each a ferric ion (Fe3+).
• the examples of the typical compounds for the chelating agents having a chelating stability constant of not less than 8 to ferric ions include those given below, provide however that the chelating agents shall have no special limitation thereto. Namely, ethylenediamine diorthohydroxy phenyl acetic acid, diaminopropane tetraacetic acid, nitrilotriacetic acid, hydroxyethylenediamine triacetic acid, dihydroxyethyl glycine, ethylenediamine diacetic acid, ethylenediamine dipropionic acid,iminodiacetic acid, diethylenetriamine pentaacetic acid, hydroxyethyl iminodiacetic acid, diaminopropanol tetraacetic acid, transcyclohexanediamine tetraacetic acid, glycolether diamine tetraacetic acid, ethylenediamine tetrakismethylene phosphonic acid, nitrilotrimethylene phosphonic acid, 1-hydroxyethylid
• diethylenetriamine pentaacetic acid nitrilotriacetic acid, nitrilotrimethylene phosphonic acid and 1-hydroxyethylidene-1,1-diphosphonic acid and, inter alia, it is preferable to use 1-hydroxyethylidene-1,1-diphosphonic acid.
• the above-given chelating agents may be used in an amount within the range of, desirably 0.01 to 50 g and, preferably 0.05 to 20 g per liter of a stabilizing solution used. When this is the case, every excellent result can be enjoyed.
• the compounds desirably added to a stabilizing solution include, for example, an ammonium compound.
• These compounds may be supplied from the ammonium salts of various kinds of inorganic compounds.
• the ammonium salts thereof include, typically, ammonium hydroxide, ammonium bromide, ammonium chloride and ammonium phosphate. These salts may be used independently or in combination.
• the ammonium compounds may be used within the range of, desirably, 0.001 to 1.0 mols and, preferably, 0.002 to 2.0 mols per liter of a stabilizer used.
• the stabilizing solution contains any one of sulfites regardless of either organic or inorganic sulfites, provided they are able to release sulfite ions.
• the inorganic sulfite salts are preferably used.
• the typical compounds thereof include, desirably, sodium sulfite, potassium sulfite, ammonium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, sodium metabisulfite, potassium metabisulfite, ammonium metabisulfite and hydrosulfite.
• the above-given sulfites may be added to a stabilizing solution in such an amount, desirably, so as to be at least 1x10 ⁇ 3 mols/liter and, preferably, within the range of 5x10 ⁇ 3 to 10 ⁇ 1 mols/liter. When this is the case, a stain prevention effect can be displayed thereby.
• the sulfites may be added directly to a stabilizing solution or, preferably, to a stabilizing replenisher.
• the stabilizing solutions contain the above-mentioned chelating agents and a metal salt in combination.
• the metal salts include, for example, those of Ba, Ca, Ce, Co, In, La, Mn, Ni, Bi, Pb, Sn, Zn, Ti, Zr, Mg, Al or Sr. These metal salts may be supplied in the form of the inorganic salts such as those of a halide, hydroxide, sulfate, carbonate, phosphate or acetate or a water-soluble chelating agent. These metal salts may be added in an amount within the range of, desirably 1x10 ⁇ 4 to 1x10 ⁇ 1 mols/liter of a stabilizer and, preferably 4x10 ⁇ 4 to 2x10 ⁇ 2 mols/liter thereof.
• a stabilizing solution may contain organic acid salts (such as citrate, acetate, succinate, oxalate and benzoate) and pH controllers (such as phosphate, borate, hydrochloric acid and sulfate).
• organic acid salts such as citrate, acetate, succinate, oxalate and benzoate
• pH controllers such as phosphate, borate, hydrochloric acid and sulfate.
• the stabilizing solutions may preferably contain a surfactant including, particularly, the compounds represented by Formula [II] given in Japanese Patent Application No. 2274026/1990, p.6.
• a surfactant including, particularly, the compounds represented by Formula [II] given in Japanese Patent Application No. 2274026/1990, p.6.
• the typical and particularly desirable examples thereof include the following water-soluble organic siloxane type compounds and, besides, it is also allowed to use the compounds represented by Formulas [I] and [II] given in JP OPI Publication No. 62-250449/1987.
• the water-soluble organic siloxane type compounds containing polyoxyalkylene groups may be added in an amount within the range of 0.01 to 20 g per liter of a stabilizing solution. In that case, they can display excellent effects.
• the surface of a subject light sensitive material is distinctively stained. If exceeding 20 g, a large amount of the organic siloxane type compounds adhere to the surface of a subject light sensitive material, so that the stains may resultingly be increased.
• silver may be recovered from a stabilizing solution used. It is also a desirable embodiment for embodying the invention to treat a stabilizing solution in an ion-exchange treatment, an electrodialysis treatment (for the details, refer to JP OPI Publication No. 61-28949/1986) or a back permeation treatment (for the details, refer to JP OPI Publication Nos. 60-241053/1985, 62-254151/1987 and 2-132440/1990). It is also desirable to use water demineralized in advance in a stabilizing solution, because the antimolding, stabilizing and image preserving properties of the stabilizing solution can be improved thereby.
• the means for the demineralizing treatments may include any one, provided that washing water can keep the Ca and Mg ions thereof having not more than 5 ppm after completing the treatment.
• the treatments are desirably carried out, independently or in combination, with an ion-exchange resin or a back permeating membrane.
• the ion-exchange resins and back permeating membranes are detailed in, for example, Open Technical Bulletin No.87-1984.
• the salt concentration is desirably not more than 1000 ppm and preferably not more than 800 ppm, from the viewpoint of displaying the effects of the invention.
• a soluble iron salt is desirably made present in the stabilizing solutions, from the viewpoint of displaying the effects of the invention.
• the above-mentioned soluble iron salts may be used in a concentration of at least 5x10 ⁇ 3 mols/liter or within the range of, desirably, 8x10 ⁇ 3 to 150x10 ⁇ 3 mols/liter and, preferably, 12x10 ⁇ 3 to 100x10 ⁇ 3 mols/liter.
• the treating temperature is within the range of, desirably, 15 to 70°C and, preferably, 20 to 55°C.
• the treating time is desirably not longer than 150 seconds or within the range of, more desirably, 3 to 120 seconds and, preferably, 6 to 90 seconds.
• a stabilizing tank may be comprised of a plurality of tanks.
• the numbers of the tanks are, desirably, not less than 2 tanks to not more than 6 tanks and, more desirably, 2 to 3 tanks.
• the stabilizing tank is preferably comprised of 2 tanks and so arranged as to be a counter-current system (that is a system in which a stabilizer is supplied from a bath behind and is then overflowed from a bath forward.)
• Any washing treatment is not required at all after completing the above-mentioned stabilizing treatment. However, it is allowed, if intended, to carry out a surface rinsing treatment with a small amount of washing water for a substantially short time.
• the bleaching agents desirably applicable to a bleaching solution or a bleach-fixing solution include, for example, the ferric complex salts of an organic acid represented by Formula [A] given below.
• A1 through A4 may be the same with or the different from each other and represent each -CH2OH, -COOM or -PO3M1M2 in which M, M1 and M2 represent each a hydrogen atom, an alkali metal atom or an ammonium group; and X represents a substituted or unsubstituted alkylene group having 3 to 6 carbon atoms.
• A1 through A4 may be the same with or the different from each other and represent each -CH2OH, -COOM or -PO3M1M2 in which M, M1 and M2 represent each a hydrogen atom, an alkali metal atom (such as a sodium atom or a potassium atom) or an ammonium group; and X represents a substituted or unsubstituted alkylene group having 3 to 6 carbon atoms (such as a trimethylene, tetramethylene or pentamethylene group).
• the substituents for the above-mentioned alkylene groups include, for example, a hydroxyl group and an alkyl group having 1 to 3 carbon atoms.
• the other typical examples of the compounds further include those of (A-2), (A-3), (A-5) through (A-8) and (A-10) through (A-12) given in JP Application No. 2-274026/1990, pp.89 ⁇ 90.
• the ferric iron complex salts of the above-given (A-1) through (A-12) the sodium salts, potassium salts or ammonium salts of these ferric iron complex salts may be used without limitation. From the viewpoints of the effects of the objects of the invention and the solubility, the ammonium salts of the ferric iron complex salts may preferably be used.
• the particularly preferable compound is A-11).
• the ammonium salts may be used in a proportion of not more than 50 mol%, desirably not more than 20 mol% and preferably not more than 10 mol%, because the oxidation of the foregoing bleaching agents are high enough and a bleach-fog is liable to produce in the case of using the ammonium salts.
• organic acid ferric iron complex salts may be added in an amount within the range of, desirably, 0.1 to 2.0 mols per liter of a bleaching solution used and, preferably, 0.15 to 1.5 mols.
• the ferric complex salts of the compounds represented by Formula [A] are to occupy desirably not less than 70% (in terms of mols), more desirably not less than 80%, particularly not less than 90% and preferably not less than 95%.
• the organic acid iron (III) complex salts may also be used either in the form of a complex salt or after the iron (III) ion complex salts are formed in a solution by making use of an iron (III) salt such as ferric sulfate, ferric chloride, ferric acetate, ferric ammonium sulfate or ferric phosphate and aminopolycarboxylic acid or the salts thereof.
• an iron (III) salt such as ferric sulfate, ferric chloride, ferric acetate, ferric ammonium sulfate or ferric phosphate and aminopolycarboxylic acid or the salts thereof.
• the complex salts may be used independently or in combination.
• the complex salts are formed in a solution by making use of ferric complex salts and aminopolycarboxylic acid
• the ferric salts may be used independently or in combination. Further, it is allowed to use the aminopolycarboxylic acids independently or in combination.
• aminopolycarboxylic acids may be used in an excess amount more than for forming iron (III) ion complex salts.
• the bleaching solution or bleach-fixing solution contains at least one of the imidazole and the derivatives thereof given in JP Application No. 63-48931/1988 or the compounds represented by Formulas [I[ through [IX] and the exemplified compounds thereof each also given in the same application, the effects of the rapid bleaching or bleach-fixing property can be displayed.
• the following compounds may also similarly be used. Namely, the exemplified compounds given in JP Application No. 60-263568/1985, pp.51 ⁇ 115; the exemplified compounds given in JP OPI Publication No. 63-17445/1988, pp.22 ⁇ 25; and the compounds given in JP OPI Publication No. 53-95630/1975 and 53-28426/1975.
• the above-given bleach accelerators may be used independently or in combination. They may be added in an amount within the range of, generally 0.01 to 100 g per liter of a bleaching solution used, desirably 0.05 to 50 g and, preferably 0.05 to 15 g.
• bleach accelerators When adding the bleach accelerators, they may be added as they are. However, they may generally be added after they are dissolved in advance in an organic acid or the like. They may also be added, if required, after dissolving them with an organic solvent such as methanol, ethanol and acetone.
• the bleaching solutions or bleach-fixing solutions may be used at a temperature within the range of 20 to 50°C and desirably 25 to 45°C.
• the pH values of the bleaching solutions may be, desirably, not higher than 6.0 and, preferably, within the range of not lower than 1.0 to not higher than 5.5.
• the pH values of the bleaching solutions are each defined as a pH of the content of a processing tank when processing a silver halide photographic light sensitive material, these pH values can clearly be distinguished from the pH values of the so-called replenishers.
• the bleaching solutions or bleach-fixing solutions are ordinarily used upon adding thereto a halide such as ammonium bromide, potassium bromide and sodium bromide. It is also allowed to contain thereto a variety of fluorescent whitening agents and defoaming agents.
• a halide such as ammonium bromide, potassium bromide and sodium bromide. It is also allowed to contain thereto a variety of fluorescent whitening agents and defoaming agents.
• the bleaching solution may be replenished in an amount of, desirably not more than 500 ml per sq.meter of a silver halide color photographic light sensitive material used, more desirably within the range of 20 ml to 400 ml and, preferably 40 ml to 350 ml.
• a suitable oxidizer such as hydrogen peroxide, a bromate and a persulfate.
• a fixing solution or a bleach-fixing solution may desirably contain at least a thiocyanate for serving as a fixing agent, and a thiosulfate and the thiocyanate may also be used in combination.
• the thiocyanates may be used in an amount of, desirably not less than 0.3 mols/liter and, preferably within the range of 0.5 to 3.0 mols/liter.
• the fixing solutions or bleach-fixing solutions each relating to the invention may be replenished in an amount of, desirably, not more than 900 ml per sq,meter of a subject light sensitive material, or within the range of, more desirably, 20 to 750 ml per sq.meter thereof and, preferably, 50 to 620 ml per sq.meter thereof.
• the pH values of the fixing solutions or bleach-fixing solutions each relating to the invention is preferably within the range of 4 to 8.
• the fixing solutions or bleach-fixing solutions are allowed to contain the compounds represented by Formula [FA] given in JP Application No. 63-48931/1988, p.56 and the exemplified compounds and, further, the compounds represented by Formula (1) or (2) given in International Publication No. WO91/08517, pp.5 ⁇ 10.
• the other effects can be so displayed as to remarkably reduce a sludge produced when a small quantity of light sensitive material is processed extending for a long time with a bleach-fixing solution or a fixing solution.
• the fixing solutions or bleach-fixing solutions may also be applied with a sulfite or a sulfite-releasing compound.
• the typical exemplified compounds thereof include, for example, potassium sulfite, sodium sulfite, ammonium sulfite, ammonium hydrogensulfite, potassium hydrogensulfite, sodium hydrogensulfite, potassium methabisulfite, sodium metabisulfite and ammonium metabisulfite.
• the compounds represented by Formula [B-1] or [B-2] given in JP Application No. 63-48931/1988, p.60 may also be included therein.
• the sulfurous acid ions thereof are required to be in an amount of at least 0.05 mols per liter of a fixing solution used or within the range of, desirably 0.10 to 0.50 mols/liter and, preferably 0.12 to 0.40 mols/liter.
• any processing time may be selected. However, it is desirably within 3 minutes 30 seconds or within the range of, more desirably 10 to 20 seconds and, preferably 20 seconds to 3 minuted.
• a stabilizing solution a processing solution having a fixing function and a bleaching solution.
• the reasons thereof are that the stirring treatments are carried out from the viewpoints not only for more excellently displaying the effects of the objects of the invention, but also for providing a rapid processing aptitude.
• the expression, '--- to forcibly stir ---' does not mean herein any ordinary liquid diffusion/transfer, but means a forcible stirring made by attaching with a stirring means.
• the stirring means the means given in JP OPI Publication Nos. 64-222259/1989 and 1-206343/1990 may be adopted.
• any one of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can desirably be used.
• the average silver iodide content of the whole silver halide emulsion is to be within the range of, desirably 0.1 to 15 mol%, more desirably 0.5 to 12 mol% and, preferably 1 to 10 mol%.
• the average grain size of the whole silver halide emulsion is to be not larger than 2.0 ⁇ m and, preferably within the range of 0.1 to 1.0 ⁇ m.
• a silver halide emulsion contains the grains having an average value of (the grain sizes/the grain thicknesses) of less than 5, it is desirable from the desilvering viewpoint that the grain size distribution thereof is monodispersive.
• a monodisperse type silver halide emulsion means that the silver halide grains, which have the grain sizes within the range of ⁇ 20% of the average grain size, occupy not less than 60%, desirably not less than 70% and preferably not less than 80% by weight of the whole silver halide grains.
• 'an average grain size' is herein defined as a grain size ri obtained when a product ni x ri3 is maximized, in which ri represents a grain size and ni represents a frequency of the grains having a grain size ri; (wherein the significant figures have each three figures and the number of the lowest figure is rounded by the fractions of 5 and over as a unit and cut away the rest.)
• the term, 'a grain size' means a grain diameter and, in the case of the other shaped grains than the globular-shaped, it means a diameter of the grain obtained when the projective image area thereof is converted into a circle having the same area.
• the above-mentioned grain sizes can be obtained in the manner, for example, that a subject grain is magnified by 10,000 to 50,000 times through an electron microscope, the magnified image thereof is photographed and either one of the printed grain diameter or the projected grain area is practically measured; (provided that the numbers of the grains subject to measurement are to be not less than 1000 pieces.
• the crystals of silver halide grains may be either regular crystals or twinned crystals and may also be those having any ratios of [1.0.0] planes to [1.1.1] planes.
• the crystal structures of the silver halide grains may be either those uniform from the inside to the outside or the layered structures different between the inside and the outside (that is so-called a core-shell type structure).
• the silver halides may also be either a type of forming a latent image mainly on the surfaces of the grains thereof or another type of forming a latent image inside the grains.
• the so-called tabular-shaped silver halide grains may also be used; (for the details, refer to JP OPI Publication No. 58-113934/1983 and JP Application No. 59-170070/1984).
• Any silver halide grains can be used therein, provided that they are prepared in any one of the preparation processes, such as an acidic process, a neutralizing process and an ammoniacal process.
• the process comprising, for example, preparing seed grains in an acidic process, growing the resulting seed grains in an ammoniacal process which is capable of making a growing rate faster and then further growing the grown grains up so as to have a specific size.
• silver ions and halide ions are gradually poured into a reaction chamber at the same time and mixed together, with controlling the pH, pAg and so forth in the reaction chamber so that the amounts of the both ions can meet the silver halide grain growing rate as described in, for example, JP OPI Publication No. 54-48521/1979.
• silver halide grains it is preferred to prepare silver halide grains in the following manner.
• the compositions containing the above-described silver halide grains are called the silver halide emulsions.
• the silver halide emulsions given in Research Disclosure No. 308119 may be used therein.
• the following table indicates where the silver halide emulsions are given in RD308119.
• a physically ripened, chemically ripened and spectrally sensitized silver halide emulsion is used.
• the additives applicable to the above-mentioned processing steps are detailed in Research Disclosure Nos. 17643, 18716 and 308119 (hereinafter abbreviated to as RD17643, RD18716 and RD308119)
• couplers may be used in the light sensitive materials applicable to the invention.
• the typical examples of the couplers are given in the above-mentioned Research Disclosures. The following table indicates where these couplers are given therein.
• the additives applicable to the invention may be added in a dispersion method detailed in RD308119, XIV and so forth.
• the supports given in the foregoing RD17643, p.28; RD18716, pp.647 ⁇ 648; and RD308119, XIX can be used.
• a light sensitive material may be provided with the filtering layers and interlayers given in the foregoing RD308119, VII-K and may also have various layer arrangements such as the normal layer arrangements, inverted layer arrangements and unit arrangements each given in the foregoing RD308119, VII-K.
• the above-mentioned vinyl sulfone type layer hardeners mean a compound having a vinyl group coupled to a sulfonyl group or a group capable of forming a vinyl group and, preferably, a compound having at least two vinyl groups each coupled to a sulfonyl group or at least two groups each capable of forming a vinyl group.
• the compounds having the following Formula [VS-I] can preferably be used in the invention.
• L represents a bonding group having m valencies
• m is an integer of 2 to 10, provided, when m is not less than 2, -SO2X may be the same with or the different from each other.
• the bonding group L having m valencies is an m valent group formed by a single bond or the combinations of the plural bonds represented by, for example, an aliphatic hydrocarbon group (such as an alkylene group, an alkylidene group, and alkylidine group or the group formed by bonding the above-given groups, an aromatic hydrocarbon group (such as an arylene group or the group formed by bonding the above-given group), -O-, -NR′- (in which R′ represents a hydrogen atom or, preferably, an alkyl group having 1 to 15 carbon atoms), -S-, >N-, -CO-, -SO-, -SO2- or -SO3-; provided that, when a bonding group L contains 2 or more -NR′-, these R′s may be bonded together to form a ring.
• an aliphatic hydrocarbon group such as an alkylene group, an alkylidene group, and alkylidine group or the group formed by bonding
• the bonding group L may include further those having a substituent such as a hydroxy group, an alkoxy group, a carbamoyl group, a sulfamoyl group, an alkyl group or an aryl group.
• the other typical exemplified compounds include (VS-1), (VS-3), (VS-5), (VS-7), (VS-8), (VS-11), (VS-13), (VS-21), (VS-23) through (VS-32), (VS-34) through (VS-53) and (VS-55) through (VS-57) each given in JP Application No. 2-274026/1990, pp.122 ⁇ 128.
• the vinyl sulfone type layer hardeners applicable to the invention include, for example; the aromatic type compounds such as those given in German Patent No. 1,100,942 and U.S. Patent No. 3,490,911; the alkyl compounds bonded to a heteroatom, such as those given in JP Examined Publication No. 44-29622/1969, 47-25373/1972 and 47-24259/1972; the sulfonamide ester type compounds such as those given in JP Examined Publication No. 47-8736/1972; 1,3,5-tris[ ⁇ -(vinyl sulfonyl)propionyl]-hexahydro-s-triazine such as those given in JP OPI Publication No.
• the aromatic type compounds such as those given in German Patent No. 1,100,942 and U.S. Patent No. 3,490,911
• the alkyl compounds bonded to a heteroatom such as those given in JP Examined Publication No. 44-29622/1969
• the above-given vinyl sulfone type layer hardeners may be dissolved in water or an organic solvent and then used in a proportion within the range of 0.005 to 20% by weight and, preferably, 0.02 to 10% by weight of a binder (such as gelatin) used. These hardeners may be added into a photographic layer in a batch system or an in-line addition system.
• the uppermost single layer, the lowermost single layer or every one of the photographic layers may be added thereby.
• a silver halide color photographic light sensitive material contains at least one kind of the compounds represented by the following Formulas [B-1] through [B-3].
• R1 represents an alkyl group, a cycloalkyl group, an aryl group, a hydroxyl group, an alkoxycarbonyl group, an amino group, a carboxylic acid group (including the salts thereof) or a sulfonic acid group (including the salts thereof);
• R2 and R3 represent each a hydrogen atom, a halogen atom, an amino group, a nitro group, a hydroxyl group, an alkoxycarbonyl group, a carboxylic acid group (including the salts thereof) or a sulfonic acid group (including the salts thereof);
• M represents a hydrogen atom, an alkali metal atom or an ammonium group.
• R4 represents a hydrogen atom, an alkyl group, an aryl group, a halogenoalkyl group, -R12-OR13, -CONHR14 (in which R12 represents an alkylene group and R13 and R14 represent each a hydrogen atom, an alkyl group or an arylalkyl group) or an arylalkyl group;
• R5 and R6 represent each a hydrogen atom, a halogen atom, a halogenoalkyl group or an alkyl group;
• R7 represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a halogenoalkyl group, an arylalkyl group, -R15-OR16 or -CONHR17 (in which R15 represents an alkylene group; and R16 and R17 represent each a hydrogen atom or an alkyl group);
• R8, R9, R10 and R11 represent each a hydrogen atom, a
• the other typical examples thereof further include (B-1-4) through (B-1-15) and (B-1-17) each given in JP Application No. 2-274026/1990, pp.130 ⁇ 132.
• the preferable compounds among the above-given exemplified compounds include, for example, (B-1-1), (B-1-2), (B-1-3), (B-1-4) and (B-1-5).
• the compounds represented by Formula [B-1], which are applicable to the invention, may be used in an amount within the range of desirably 0.03 to 50 g per liter of the stabilizer of the invention used, more desirably, 0.12 to 10 g and, preferably, 0.15 to 5 g.
• the compounds represented by Formulas [B-1] through [B-3] may be used in an amount within the range of 0.1 to 500 mg and, preferably, 0.5 to 100 mg per sq.meter of a light sensitive materials used.
• the compounds represented by formulas [B-1] through [B-3] may be used independently or in combination.
• the invention can be applied to color photographic light sensitive materials including, for example, a color paper, a color negative film, a color reversal film, a color reversal paper, a direct positive paper, a cinematographic color film and a TV color film, each for general or cinematographic use.
• a multilayered color photographic light sensitive material was prepared by forming the layers having the following compositions on a triacetyl cellulose film support, in the order from the support side.
• the amounts of the materials added to a subject silver halide photographic light sensitive material are indicated by grams per sq.meter unless otherwise expressly stated.
• the amounts of silver halide and colloidal silver are indicated by converting them into the silver contents.
• the sensitizing dyes used therein are indicated by the mol numbers per mol of silver halides contained in one and the same layer.
• Layer 3 A low-speed red-sensitive emulsion layer
• Layer 4 A medium-speed red-sensitive emulsion layer
• Layer 5 A high-speed red-sensitive emulsion layer
• Layer 7 A low-speed green-sensitive emulsion layer
• Layer 8 A medium-speed green-sensitive emulsion layer
• Layer 9 A high-speed green-sensitive emulsion layer
• Layer 11 A low-speed blue-sensitive emulsion layer
• Layer 12 A high-speed blue-sensitive emulsion layer
• compositions Besides the above-given compositions, coating aid Su-1, Dispersing aid Su-2, a viscosity controller, layer hardeners H-1 and H-2, stabilizer ST-1, antifoggant AF-1 and two kinds of antifoggant AF-2 having Mw: 100000 and Mw: 1100000 were each added.
• the emulsions applied to the above-described samples were the monodisperse emulsions having a low silver iodide content on the surfaces of the emulsion grains and they were subjected to the optimum gold-sulfur sensitization in an ordinary method.
• the average grain size thereof were indicated by the grain sizes converted into a cube.
• Weight average molecular weight: Mw 3000
• the resulting film samples were exposed practically to light through a camera and the exposed film samples were then subjected to running tests by varying the stabilizer replenished amounts as shown in Tables 4 and 5, under the following conditions.
• the stabilizing step was carried out in a dual tank counter-current system in which the replenishment was made to the final stabilizing solution tank and the overflow was so flowed into the tank precedent to the final stabilizing solution tank. Further, a part of the overflow (in a proportion of 275 ml/m2) was flowed from the stabilizing tank following the fixing tank into the fixing tank.
• compositions of the processing solutions used in the above-mentioned processing steps were as follows.
• magenta density in the maximum density area was measured and, after each film sample was stored for 10 days under the conditions of 70°C and 70%RH, the resulting maximum magenta density was measured so that the dye discoloration ratios were obtained. The results thereof are shown collectively in tables 4 and 5.
• magenta discoloring ratios were the same.
• the sulfide precipitates, cotton-like suspended matters and the stains, scratches and foreign matter adhesion found after treatments were each proved to be O, so that the invention could be more improved.
• the invention could be proved to be excellent in the solution preservability even if the aperture area should be widened.
• the process for a silver halide color photographic light sensitive material which is capable of not only providing stable processing characteristics even when a low replenishment is made to a stabilizing solution and disusing any conventional formaldehyde, but also preventing the productions of any sulfide precipitates in a stabilizing bath, any cotton-like suspended matters, any tar and any fixed adhesion to the walls of the stabilizing tank and, further, capable of positively preventing the productions of any tar, scratches and foreign matter adhesion after completing drying step.

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