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
  • G03C7/42—Bleach-fixing or agents therefor ; Desilvering processes

Definitions

• This invention relates to a bleach-fixing solution, and particularly to a bleach-fixing solution that can achieve rapid processing when applied in a light-sensitive material for photographing.
• the desilvering of light-sensitive materials for photographing in which a highly sensitive silver iodobromide-rich emulsion is used is carried out separately in a bleaching step and a fixing step.
• DTPA ' Pe complex salt a diethylenetriaminepentaacetic acid ferric complex salt
• DTPA ' Pe complex salt a diethylenetriaminepentaacetic acid ferric complex salt
• the above DTPA ⁇ FE complex salt can satisfy the above properties when used in the higher pH range, specifically, at about pH 7 to 9.
• ammonia gas may be readily generated when used in such a pH range, so that there has been a problem undesirable from a viewpoint of the work environment if the developing is carried out in a small room.
• the present inventors have continued further studies to find, as a result, that the lowering of the desilvering ability and the inferiority in the color reproduction that are considered to be caused by the above-mentioned accumulation of ferrous ions can be solved at the same time and the problem of the generation of ammonia gas can be solved by using a bleach-fixing solution having the pH in a particular lower range and containing a particular aminopolycarboxylic ferric complex salt.
• Some compounds of the compounds represented respectively by General Formulas (II) and (III) of this invention are known to be used in a bleach-fixing solution containing an ethylenediaminetetraacetic acid iron (III) complex (hereinafter "EDTA ⁇ Fe) as a bleaching agent, as disclosed, for example, in Japanese Publication No. 38895/1979.
• EDTA ⁇ Fe ethylenediaminetetraacetic acid iron
• it was revealed that such compounds may gradually release sulfite ions when used in the bleach-fixing solution containing the above EDTA-F E , so that aldehydes or ketones may be accumulated and the desilvering speed may be gradually lowered.
• a first object of this invention is to provide a bleach-fixing solution made feasible for rapid processing of a light-sensitive photographic material for photographing.
• a second object of this invention is to provide a bleach-fixing solution free from generation of ammonia gas and desirable from the viewpoint of work environment.
• a third object of this invention is further to provide a bleach-fixing solution that can delay the occurrence of the precipitation even during storage with time to attain a stable bleach-fixing performance.
• a fourth object of this invention is to provide a bleach-fixing solution that can improve the bleach stain at a non-image portion of a light-sensitive material when the processing with low replenishment is carried out.
• a bleach-fixing solution for processing a light-sensitive silver halide photographic material for photographing, wherein said solution has the pH ranging between 3.0 and 6.8, contains a ferric complex salt having a ligand comprising a compound represented by General Formula (I) shown below, and further contains at least one of;
• the ferric complex salt having a ligand comprising the compound represented by General Formula (I) is used.
• R 1 may preferably be a hydrogen atom. Also, the total sum of the carbon atom number in may most preferably be 3.
• the ferric complex salt having a ligand comprising the compound represented by the above General Formula (I) may be used also in the form of a free acid (hydrogen salt), or may also be used in the form of a counter salt including alkali metal salts such as a sodium salt, a potassium salt and a lithium salt or an ammonium salt, or water soluble amines, for example, triethanolamine, etc.
• a counter salt including alkali metal salts such as a sodium salt, a potassium salt and a lithium salt or an ammonium salt, or water soluble amines, for example, triethanolamine, etc.
• Preferably used are a potassium salt, a sodium salt and an ammonium salt.
• At least one of these ferric complex salts of this invention may be used, but two or more of these can also be used in combination. It is also possible to use them in combination with any ferric complex salts outside this invention.
• ferric complex salts of this invention as exemplified in the above, preferred are ferric complex salts in which any of exemplary compounds (I-I), (I-2) and (I-3) is used as the ligand. Still among these exemplary compounds (I-I), (I-2) and (I-3), it is particularly preferred to use (I-I) or (I-2) from a viewpoint of the solubility, and, taking account of various points such as the effect aimed at in this invention, it is most preferred in this invention to use (I-I).
• the ferric complex salt can be used in any amount in the bleach-fixing solution of this invention so long as it is in an amount sufficient for obtaining the effect of this invention.
• overly high concentration of the ferric complex salt may cause the deterioration of shelf stability of the bleach-fixing solution, and, on the other hand, overly low concentration of the ferric complex salt may cause the deterioration of desilvering performance and color reproduction performance.
• it may be usually used preferably in the range of 0.02 to 1.30 mol/lit., more preferably 0.10 to 1.20 mol/lit.
• the effect of this invention can be preferably exhibited when used in the range of 0.20 to 0.80 mol/lit.
• the bleach-fixing solution of this invention may be appropriately in the pH range of pH 3.0 to 6.8, because sulfite gas may be generated at less than pH 3.0 and the effect of this invention may be insufficient if the pH is higher than 6.8. It can be used at any pH so long as it is used in this pH range, but is preferably used at pH 4.0 to 6.7, particularly preferably pH 5.0 to 6.5, taking account of the solubility of various iron salts at low temperature the odor of the sulfite gas generated from sulfite ions in addition to desilvering performance and color reproduction.
• the bleach-fixing solution of this invention may preferably contain a variety of sulfites therein, and these sulfites may include ammonium sulfite, sodium sulfite, potassium sulfite, sodium hydrogensulfite, potassium hydrogensulfite, sodium metabisulfite, etc.
• At least one compound selected from the compounds represented respectively by General Formulas (II) and (III) may be used as a preservative in the bleach-fixing solution of this invention.
• the alkyl group having 1 to 8 carbon atoms may preferably include an alkyl group having 1 to 4 carbon atoms.
• One of the preferred compounds included in the carbonyl bisulfite addition compound represented by General Formula (II) is a compound wherein R2is a hydrogen atom and R 3 is an alkyl group having 1 to 4 carbon atoms, and another of them is a compound wherein R 2 and R 3 each are an alkyl group having 1 to 4 carbon atoms.
• the alkyl group having 1 to 8 carbon atoms may preferably include an alkyl group having 1 or 2 carbon atoms.
• n which represents an integer of 0 to 6, may preferably be an integer of 1 to 4.
• One of the preferred compounds included in the carbonyl bis-bisulfite addition compound represented by General Formula (III) is a compound wherein R 4 and R 5 each are a hydrogen atom and n is an integer of 1 to 4. Another of them is a compound wherein R 4 and R 5 each are an alkyl group having 1 or 2 carbon atoms and n is an integer of 1 to 4.
• the above bisulfite addition compound of this invention may be used by using one kind thereof alone or two or more thereof in combination, and can be used in an amount of 0.01 mol to 2 mols, preferably 0.02 to 1 mol, and more preferably 0.05 to 0.5 mole, per liter of the bleach-fixing solution of this invention.
• the polymer having a unit of a pyrrolidone nucleus in the molecular structure (hereinafter called "vinyl pyrrolidone polymer of this invention") will be described below.
• the vinyl pyrrolidone polymer of this invention may comprise either a homopolymer of vinyl pyrrolidone alone or a copolymer thereof with additional copolymerizable monomer(s), but it is required to be water-soluble as a polymer.
• the above additional monomer copolymerizable with vinyl pyrrolidone may typically include, for example, vinyl esters, acrylates, methacrylates, acrylic acids, methacrylic acid, styrene, etc.
• the vinyl esters may include, for example, vinyl acetate, vinyl propionate, vinyl butyrate.
• the acrylic esters may include, for example, methyl ester, ethyl ester, butyl ester, 2-ethyl hexyl ester, etc.
• the copolymerization ratio may preferably be selected in the range of 5 to 100 mol % based on the vinyl pyrrolidone.
• the average molecular weight of the vinyl pyrrolidone polymer of this invention may preferably in the range of 500 to 800,000, more preferably 2,000 to 400,000.
• the determination of the average molecular weight of the polymer can be carried out according to a usual method, for example, according to the following:
• the value K is determined according to Fikentscher's viscosity formula (see Physikalische U. Technsammlung Prufungsvon fur Lacke und Hä Rohstoffe, 1953 Edit.), and the average molecular weight is determined from the value K according to a usual method.
• Typical examples of the vinyl pyrrolidone polymer of this invention are shown below, but by no means limited to these.
• the amount for the addition of the above vinyl pyrrolidone polymer of this invention may vary depending on the type of the polymer, the polymerization degree and so forth, but approximately may preferably in the range of 0.1 to 100 g, more preferably 0.2 to 50 g, still more preferably 0.3 to 20 g, and particularly preferably 0.5 to 10 g, per liter of the bleach-fixing solution of this invention.
• the vinyl pyrrolidone polymer of this invention may be added in the bleach-fixing solution by, for example, adding it directly as it is in the form of powder, or may be added by dissolving it in a solvent such as water.
• the above vinyl pyrrolidone polymer of this invention may be more preferably used for the purpose of better improving the shelf stability of the bleach-fixing solution, when a sulfite or a sulfite-releasable compound (for example, carbonyl bisulfite addition compounds disclosed in Japanese Patent Publication No. 38895/1979) is used in combination with it.
• a sulfite or a sulfite-releasable compound for example, carbonyl bisulfite addition compounds disclosed in Japanese Patent Publication No. 38895/1979
• the sulfite or the sulfite-releasable compound may preferably be contained in an amount of 1 x 10- 3 mol or more per liter of the bleach-fixing solution of this invention. It may be used more preferably in an amount of not less than 0.02 mol and not more than 2.0 mols, still more preferably not less than 0.05 mol and not more than 1.3 mols, and most preferably not less than 0.09 mol and not more than 0.9 mol.
• the above sulfite may include ammonium sulfite, sodium sulfite, potassium sulfite, sodium hydrogensulfite, potassium hydrogensulfite, sodium metabisulfite, etc.
• Embodiment iii) of this invention will be described below. Preferred examples of the compounds represented respectively by General Formulas (IV) to (VII), used in embodiment iii) are shown below.
• the ferric complex salt having a ligand comprising at least one of the compounds represented respectively by General Formulas (IV) to (VII) may be used also in the form of a free acid (hydrogen salt), or may also be used in the form of a counter salt including alkali metal salts such as a sodium salt, a potassium salt and a lithium salt or an ammonium salt, or water soluble amine salts, for example, triethanolamine salt, etc.
• alkali metal salts such as a sodium salt, a potassium salt and a lithium salt or an ammonium salt, or water soluble amine salts, for example, triethanolamine salt, etc.
• Preferably used are a potassium salt, a sodium salt and an ammonium salt.
• the ferric complex salt having a ligand comprising the compound represented by General Formula (I) and ferric complex salt having a ligand comprising at least one of the compounds represented respectively by General Formulas (IV) to (VII) of this invention may preferably be in the range of 1 mol % to 95 mol %, more preferably 5 mol % to 90 mol %, and most preferably 10 mol % to 80 mol %, based on the total amount of these.
• the ferric complex salt having a ligand comprising the compound represented by General Formula (I) and that having a ligand comprising at least one compound selected from the compounds represented respectively by General Formulas (IV) to (VII) of this invention can be used in any amount in the bleach-fixing solution of this invention so long as it is in an amount sufficient for obtaining the effect of this invention.
• overly high concentration-of the ferric complex salt may cause the deterioration of shelf stability of the bleach-fixing solution, and, on the other hand, overly low concentration of the ferric complex salt may cause the deterioration of desilvering performance and color reproduction performance.
• the effect of this invention can be preferably exhibited when used in the range of 0.20 to 0.80 mol/lit.
• ferric complex salt having a ligand comprising the compound represented by General Formula (I) and ferric complex salt having a ligand comprising at least one compound selected from the compounds represented respectively by General Formulas (IV) to (VII) of this invention are used in combination, so that the shelf stability can be improved while maintaining the good desilvering and color reproduction performances inherent in the bleach-fixing solution of this invention.
• the bleach-fixing solution of the present embodiment may preferably contain a sulfite and/or a sulfite-releasable compound in order to further improve the shelf stability.
• a sulfite and/or a sulfite-releasable compound may include ammonium sulfite, sodium sulfite, potassium sulfite, sodium hydrogensulfite, potassium hydrogensulfite, sodium metabisulfite, formaldehyde bisulfite addition compounds, etc.
• These compounds may be used in an amount of 0.001 mol to 2.0 mols, preferably 0.001 mol to 1.3 mols, most preferably 0.01 mol to 0.9 mol, per liter of the bleach-fixing solution of this invention.
• the silver halide fixing agent to be contained in the bleach-fixing solution of this invention may include a compound capable of forming a water-soluble complex salt through the. reaction with the silver halide used in usual fixing, typically including, for example, thiosulfates such as potassium thiosulfate, sodium thiosulfate and ammonium thiosulfate, thiocyanates such as potassium thiocyanate, sodium thiocyanate and ammonium thiocyanate, thioureas, thioethers, highly concentrated bromides, iodides, etc.
• These fixing agents can be used in an amount of not less than 5 g/lit., preferably not less than 50 g/lit - , or more preferably not less than 70 g/lit. and in the amount of the range they can be dissolved.
• the bleach-fixing solution of this invention may contain various additives.
• the additives are alkali halides or ammonium halides, for example, potassium bromide, sodium bromide, sodium chloride, ammonium bromide, potassium iodide, sodium iodide, ammonium iodide, etc.
• the bleach-fixing solution of this invention may contain, alone or in combination of two or more of, pH buffering agents including boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide, etc. It may further contain every kind of brightening agents, anti-foaming agents, surface active agents and mildewproofing agents.
• pH buffering agents including boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide, etc. It may further contain every kind of brightening agents, anti-foaming agents, surface active agents and mildewproofing agents.
• organic chelating agents such as acetyl acetone, phosphonocarboxylic acid, polyphosphoric acid, organic phosphonic acid, oxycarboxylic acid, polycarboxylic acid, dicarboxylic acid and aminopolycarboxylic acid, stabilizers such as nitroalcohol and nitrate, solubilizing agents such as alkanolamine, anti-stain agents such as organic amine, other additives, and organic solvents
• a bleach accelerator may preferably be used in the bleach-fixing solution of this invention.
• the compounds described in Japanese Unexamined Patent Publication No. 19851/1987 and, to exhibit the effect of this invention with good results, the compounds represented respectively by General Formulas (A-I) to (A-Iv) shown below.
• Q 1 represents a group of atoms necessary for the formation of a nitrogen-containing heterocyclic ring (including those condensed with a saturated or unsaturated ring of 5 or 6 members);
• R1 represents a hydrogen atom, an alkali metal atom, or an alkyl group, provided that Q' have the same meaning as defined for Q 1 .
• R 2 and R3 each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyl group, a carboxyl group, an amino group, an acyl group having 1 to 3 carbon atoms, an aryl group or an alkenyl group.
• R and R' each have the same meaning as R 2 and R 3
• X' have the same meaning as X
• Z represents a hydrogen atom, an alkali metal atom, an ammonium group, an amino group, a nitrogen-containing heterocyclic group, an alkyl group or M represents a divalent metal atom
• R" represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group, an aryl group, a heterocyclic residual group (including those condensed with an unsaturated ring of 5 or 6 members) or an amino group
• n 1 to n 6 and m 1 to m 5 each represent an integer of 1 to 6.
• B represents an alkylene group having 1 to 6 carbon atoms
• Y represents or R 4 and R 5 each have the same meaning as R 2 and R 3 , provided that R 4 and R 5 each may represent -B-SZ, or R 2 and R 3 , and R 4 and R 5 each may combine to form a ring.
• the compound represented by the above formula may include compounds of enol form and salts thereof.
• R 6 and R 7 each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyl group, a carboxyl group, an amino group, an acyl group having 1 to 3 carbon atoms, an aryl group, an alkenyl group or -B 1 -S-Z 1 , provided that R 6 and R 7 may combine to form a ring.
• Y 1 represents or B 1 represents an alkylene group having 1 to 6 carbon atoms;
• Z 1 represents a hydrogen atom, an alkali metal atom, an ammonium group, an amino group, a nitrogen-containing heterocyclic residual group, or and n 7 represents an integer of 1 to 6.
• Ar represents a divalent arylene group or a divalent organic group comprising the combination of an aryl group with an oxygen atom and/or an alkylene group
• B 2 and B 3 each represent a lower alkylene group
• R 8 , R 9 , R 10 and R 11 each represent a hydroxyl-substituted lower alkyl group
• x and y each represent 0 or 1.
• G' represents an anion
• z represents 0, 1 or 2.
• the bleaching accelerator may preferably added in an amount ranging from about 0.01 to 100 g, more preferably 0.05 to 50 g, and particularly preferably 0.05 to 15 g, per liter of the bleach-fixing solution of this invention.
• the bleach-fixing solution of this invention can preferably be also applied in the low replenishment processing.
• iodide ions are accumulated in the bleach-fixing solution of this invention.
• the bleach-fixing solution of this invention may cause substantially no lowering of the desilvering performance even by the accumulation of iodide ions, but also it may hardly cause surprisingly any density increase at a non-image portion (the so-called fogging) also when a light-sensitive material is dipped in the bleach-fixing solution without taking the step of rinsing such as washing with water after color developing processing.
• the iodide ions may preferably be contained in the bleach-fixing solution in an amount of not less than 0.0005 mol/lit. More preferably, it may preferably contained in the bleach-fixing solution in an amount of not less than 0.001 mol/lit.
• the processing time when using the bleach-fixing solution of this invention may be not longer than 3 minutes and 30 seconds without any problem, but may preferably be not longer than 3 minutes, more preferably in 2 minutes and 30 seconds.
• the bleach-fixing solution of this invention may be used. at a temperature of 80°C or less, desirably 55 0 C or less, and most preferably 45 0 C or less. It can also desirably be used while suppressing evaporation or the like.
• the bleach-fixing solution of this invention can be applied in any light-sensitive silver halide photographic materials so long as they are light-sensitive photographic materials for photographing.
• they may preferably be light-sensitive materials employing a highly sensitive silver iodobromide emulsion having a silver iodide content of not less than 0.5 mol %, more preferably not less than 1 mol % per liter.
• the bleach-fixing solution of this invention may be used as a processing solution for bleach-fixing immediately after the color developing of the above light-sensitive silver halide photographic material for photographing, or, alternatively, used as a bleach-fixing solution after the color developing and after the processing such as washing, rinsing or stopping, or further may be used as a bleach-fixing solution after the pre-fixing was carried out after the color developing.
• the processing by use of the bleach-fixing solution of this invention may be also followed by washing with water, and thereafter may be followed by stabilizing. It can be also applied in the multi-step counter current stabilizing technique in which the washing step is omitted or the amount of water for the washing is extremely reduced as disclosed in Japanese Unexamined Patent Publication No.
• the silver halide emulsion for photographing that can be applied in this invention can be chemically sensitized according to a conventional method, and can be optically sensitized to a desired wavelength region by using a sensitizing dye.
• An antifoggant, a stabilizer and so forth can be added in the silver halide emulsion.
• a binder for the emulsion gelatin can be used advantageously.
• Emulsion layers and other hydrophilic colloid layers can be hardened, and also can contain a plasticizer, a dispersion of a water-soluble or slightly soluble synthetic polymer (i.e., latex).
• Couplers can be used in the emulsion layers of a light-sensitive color photographic material.
• a compound capable of releasing photographically useful fragments such as development accelerators, bleaching accelerators, developers, silver halide solvents, color torning agents, hardening agents, fogging agents, antifoggants, chemical sensitizers, spectral sensitizers and desensitizers through the coupling with a colored coupler, a competing coupler and an oxidized product of a developing agent.
• the light-sensitive material can be provided with auxiliary layers such as a filter layer, a halation-preventive layer and an irradiation-preventive layer. These layers and/or emulsion layers may also contain a dye that may flow out from the light-sensitive material or may be bleached during development processing.
• a matte agent, a lubricant, an image-stabilizing agent, a surface active agent, a color fog preventive agent, a development accelerator, a development retarder or a bleaching accelerator may be added in the light-sensitive material.
• a support there can be -used paper laminated with polyethylene or the like, a polyethylene terephthalate film, baryta paper, cellulose triacetate, etc.
• a halation-preventive layer and a gelatin layer were provided, and coated thereon were a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, a filter layer containing yellow colloidal silver, and a blue-sensitive silver halide emulsion layer so as to give a total silver amount of 88 mg per 100 cm 2 .
• the above emulsion layers comprised silver iodobromide having silver iodide mol % of about 4.3 %, and there were used the following (Y-I) as a yellow coupler in the blue-sensitive silver halide emulsion layer, the following (M-1) as a magenta coupler in the green-sensitive silver halide emulsion layer, and the following (C-l) as a cyan coupler in the red-sensitive silver halide emulsion layer.
• a sensitizing dye, a hardening agent and a spreading agent were added to the respective emulsion layers.
• a light-sensitive silver halide color negative materials thus prepared was used as a sample.
• the bleach-fixing solutions available after the above processing were stored with time for 1 week at 38°C under the open ratio of 10 cm 2 /lit. (which is the open condition corresponding to that of usual automatic processing machine, and meant that the solution has an air contact area of 10 cm 2 based on 1 liter of the bleach-fixing solution), and the above processing was again repeated with use of the bleach-fixing solutions available after storage.
• the residual silver amount (mg/dm 2 ) at the maximum density portion of the film samples was measured according to a fluorescent X-ray method, and the cyan dye density was further measured with use of Sakura Photoelectric Densitometer PDA-65 (produced by Konishiroku Photo Industry Co., Ltd.) to determine the color reproduction percentage.
• bleach-fixing solutions Nos. 1-1 and 2-1 used in the above Experiment 1 the types of the preservatives in the bleach-fixing solutions and the concentration for the addition were changed as shown in Table 3 below and the pH was adjusted to 6.0, to prepare bleach-fixing solutions Nos. 9-1 to 9-3 and Nos. 10-1 to 10-3.
• the above bleach-fixing solutions the light-sensitive materials corresponding to those in Experiment 1 were processed, and the resulting bleach-fixing solutions having been used for the processing were stored with time in the same manner as in Experiment 1.
• the desilvering performance and color reproduction performance were measured in the same manner as in Experiment 1 to obtain the results shown together in Table 3.
• the bleach-fixing solutions according to this invention in other words, the bleach-fixing solutions having the pH ranging between 3.0 and 6.8, containing a ferric complex salt having a ligand comprising a compound represented by General Formula (I), and further containing the bisulfite addition compound of this invention can have a good desilvering performance particularly even after storage with time, can favorably prevent color reproduction inferiority from being occurred, and can have good shelf stability.
• the bleach-fixing solutions of this invention had no ammoniacal odor at all.
• Bleach-fixing solutions were stored with time in the same manner as in Experiment 1 of Example 1.
• the bisulfite addition compound and exemplary compound No. II-4 in the bleach-fixing solutions were used in concentration of 0.25 mol/lit.
• the types of the bleaching agents were selected as shown in Table 4, and the concentration of the bleaching agents was varied as shown in Table 4.
• the pH of the bleach-fixing solutions was adjusted to 6.0.
• Bleach-fixing solutions were stored with time in the same manner as in Experiment 1 of Example 1.
• the preservative in bleach-fixing solution No. 1-1 used in Experiment 1 of Example 1 was replaced by exemplary compound No. II-6 (concentration: 0.2 mol/lit), the bleaching agent and the amount thereof were changed as shown in Table 5, and the concentration of KI in the bleach-fixing solutions was varied as shown in Table 5
• the pH of the bleach-fixing solutions was adjusted to 6.0.
• the samples having been processed were also subjected to bleaching and fixing according to the CNK-4 standard processing (color negative processing by Konishiroku Photo Industry Co., Ltd.), and, after the residual silver was perfectly removed by carrying out bleaching and fixing, transmission density of magenta dyes was measured. The value obtained was designated as D R1 .
• D R1 transmission density of magenta dyes of the samples subjected to bleaching and fixing according to the CNK-4 standard processing was measured, and the resulting value was designated as D R2 .
• the difference between D R1 and D R2 was determined ( ⁇ D R ) to evaluate the magenta stain.
• Bleach-fixing solutions Nos. 1-11 to 1-16 and Nos. 2-21 to 2-26 were prepared in the same manner as in Experiment 1 of Example 1 except that, in the bleach-fixing solutions No. 1-1 and No. 2-1 prepared in Experiment 1 of Example 1, the pH was adjusted to 6.0, exemplary compound No. II-4 (concentration: 0.1 mol/lit.) was used as the preservative, and the bleaching accelerator was added as shown in Table 6 below.
• a halation-preventive layer and a gelatin layer were provided, and coated thereon were a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, a filter layer containing yellow colloidal silver, and a blue-sensitive silver halide emulsion layer so as to give a total silver amount of 90 mg per 100 cm 2 .
• the above emulsion layers comprised silver iodobromide having silver iodide mol % of about 4.1 %, and there were used the above (Y-l) as a yellow coupler in the blue-sensitive silver halide emulsion layer, the above (M-l) as a magenta coupler in the green-sensitive silver halide emulsion layer, and the above (C-l) as a cyan coupler in the red-sensitive silver halide emulsion layer.
• conventional additives such as a sensitizing dye, a hardening agent and a spreading agent were added.
• a light-sensitive silver halide color negative materials thus prepared was used as a sample.
• the bleach-fixing solutions available after the above processing were stored with time for 1 week at 38°C under the open ratio of 10 cm 2 /lit. (which is the open condition corresponding to that of usual automatic processing machine, and meant that the solution have an air contact area of 10 cm 2 based on 1 liter of the bleach-fixing solution), and the above processing was again repeated with use of the bleach-fixing solutions available after storage.
• the residual silver amount (mg/dm 2 , at the maximum density portion of the film samples (the respective samples available before and after the storage with time, of the bleach-fixing solutions) was measured according to a fluorescent X-ray method, and the cyan dye density was further measured with use of Sakura Photoelectric Densitometer PDA-65 (produced by Konishiroku Photo Industry Co., Ltd.) to determine the color reproduction percentage.
• Results obtained are shown in Table 8 together. It is understood from the above Table 8 that in the case the bleach-fixing solutions with pH range of 3.0 to 6.8 are used with use of the organic acid ferric complex salt according to this invention, there is seen only small residual silver and good color reproduction percentage regardless of whether the solutions were stored with time. In particular, good results are obtained when the pH is 4.0 to 6.7, and particularly good results are obtained when the pH is 5.0 to 6.5.
• Exemplary vinyl pyrrolidone polymer (2) in bleach-fixing solution No. 13 used in the above Experiment 1 was changed for a control, exemplary vinyl pyrrolidone polymers Nos. (1), (3) and (5), respectively, and the pH was adjusted to 6.0, to prepare bleach-fixing solutions Nos. 16-1 to 16-5.
• Light-sensitive materials corresponding to those in Experiment 1 and employing the above bleach-fixing solutions were processed, and the resulting bleach-fixing solutions having been used for the processing were stored with time in the same manner as in Experiment 1.
• the desilvering performance and color reproduction performance were measured in the same manner as in Experiment 1 to obtain the results shown together in Table 9.
• the bleach-fixing solutions according to this invention in other words, the bleach-fixing solutions having the pH ranging between 3.0 and 6.8, containing a ferric complex salt having a ligand comprising a compound represented by General Formula (I), and further containing polyvinyl pyrrolidone of this invention can have a good desilvering performance particularly even after storage with time, can favorably prevent color reproduction inferiority from being occurred, and can have good shelf stability.
• the bleach-fixing solutions of this invention had no ammoniacal odor at all.
• Bleach-fixing solutions were stored with time in the same manner as in Experiment 1 of Example 5.
• the ammonium sulfite concentration in the bleach-fixing solutions was controlled to 12 g/lit.
• the types of the bleaching agents were selected as shown in Table 10, and the concentration of the bleaching agents was varied as Shown in Table 10.
• the pH of the bleach-fixing solutions was adjusted to 6.0.
• Bleach-fixing solutions were stored with time in the same manner as in Experiment 1 of Example 5.
• the bleaching agent in bleach-fixing solution No. 11-1 used in Experiment 1 of Example 5 as the bleach-fixing solution and the amount thereof were changed as shown in Table 11, and the concentration of KI in the bleach-fixing solutions was varied as shown in Table 11 .
• the pH of the bleach-fixing solutions was adjusted to 6.0.
• the samples having been processed were also subjected to bleaching and fixing according to the CNK-4 standard processing (color negative processing by Konishiroku Photo Industry Co., Ltd.), and, after the residual silver was perfectly removed by carrying out bleaching and fixing, transmission density of magenta dyes was measured. The value obtained was designated as D R1 .
• D R1 transmission density of magenta dyes of the samples subjected to bleaching and fixing according to the CNK-4 standard processing was measured, and the resulting value was designated as D R2 .
• the difference between D R1 and D R2 was determined ( ⁇ D R ) to evaluate the magenta stain.
• Bleach-fixing solutions Nos. 11-11 to 11-16 and Nos. 13-32 to 13-37 were prepared in the same manner as in Experiment 1 of Example 5 except that, in the bleach-fixing solutions No. I1-1 and No. 13-1 prepared in Experiment 1 of Example 5, the pH was adjusted to 6.0 and the bleaching accelerator was added as shown in Table 12 below.
• a halation-preventive layer and a gelatin layer were provided, and coated thereon were a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, a filter layer containing yellow colloidal silver, and a blue-sensitive silver halide emulsion layer so as to give a total silver amount of 93 mg per 100 cm 2 .
• the above emulsion layers comprised silver iodobromide having silver iodide mol % of about 5.0 %, and there were used the above (Y-l) as a yellow coupler in the blue-sensitive silver halide emulsion layer, the above (M-l) as a magenta coupler in the green-sensitive silver halide emulsion layer, and the above (C-l) as a cyan coupler in the red-sensitive silver halide emulsion layer.
• a sensitizing dye, a hardening agent and a spreading agent were added to the respective emulsion layers.
• a light-sensitive silver halide color negative materials thus prepared was used as a sample.
• the bleach-fixing solutions available after the above processing were stored with time for 1 week at 38 0 C under the open ratio of 10 cm 2 /lit. (which is the open condition corresponding to that of usual automatic processing machine, and meant that the solution have an air contact area of 10 cm 2 based on 1 liter of the bleach-fixing solution, and the above processing was again repeated with use of the bleach-fixing solutions available after storage.
• the residual silver amount (mg/dm 2 ) at the maximum density portion of the film samples was measured according to a fluorescent X-ray method, and the cyan dye density was further measured with use of Sakura Photoelectric Densitometer PDA-65 (produced by Konishiroku Photo Industry Co., Ltd.) to determine the color reproduction percentage.
• the concentration and combination of the ferric complex salt comprising the organic acid in bleach-fixing solution No. 19 used in the above Experiment 1 was varied as shown in Table 15 below to prepare bleach-fixing solutions Nos. 22-1 to 24-10.
• the light-sensitive materials corresponding to those in Experiment 1 were processed, and the resulting bleach-fixing solutions having been used for the processing were stored with time in the same manner as in Experiment 1.
• the desilvering performance and color reproduction performance were measured in the same manner as in Experiment 1 to obtain the results shown together in Table 15.
• Results obtained are shown together in Table 16.
• Table 16 it is understood that only the combination of the organic acid ferric complex salts of this invention can show good desilvering performance, color reproduction performance and shelf stability. It is also understood that there can be exhibited higher effect of improving the shelf stability particularly in the combination of I-1 with VI-3 or VI-7, the combination of I-2 with VI-3 or VI-7, and the combination of I-3 with VI-3 or VI-7, and preferred are the combination of I-1 with VI-7 and the combination of I-2 with VI-7.
• Results obtained are shown together in Table 17. As will be clear from Table 17, it is understood that substantially good results can be obtained when the ferric complex salt of organic acid VI-7 is used in the range of 1 mol % to 95 mol %, and goods results for all the desilvering, color reproduction and storage performances can be obtained particularly when it is used in the range of 5 mol % to 90 mol %, more particularly 10 mol % to 80 mol %.
• the bleach-fixing solutions according to this invention in other words, the bleach-fixing solutions having the pH ranging between 3.0 and 6.8, containing a ferric complex salt having a ligand comprising a compound represented by General Formula (I), and further containing a ferric complex salt having a ligand comprising at least one compound selected from the compounds represented respectively by General Formulas of General Formulas (IV) to (VII) can have a good desilvering performance particularly even after storage with time, can favorably prevent color reproduction inferiority from being occurred, and can have good shelf stability.
• the bleach-fixing solutions of this invention had no ammoniacal odor at all.
• the samples having been processed were also subjected to bleaching and fixing according to the CNK-4 standard processing (color negative processing by Konishiroku Photo Industry Co., Ltd.), and, after the residual silver was perfectly removed by carrying out bleaching and fixing, transmission density of magenta dyes was measured. The value obtained was designated as D R1 .
• the transmission density of magenta dyes of the samples subjected to bleaching and fixing according to the CNK-4 standard processing was measured, and the resulting value was designated as D R2 .
• the difference between DR1 and D R2 was determined (6D R ) to evaluate the magenta stain. Results obtained are shown together in Table 19.
• Bleach-fixing solutions Nos. 17-21 to 17-26 and Nos. 19-31 to 19-36 were prepared in the same manner as in Experiment 1 of Example 9 except that, in bleach-fixing solutions No. 17-1 and No. 19-1 prepared in Experiment 1 of Example 9, the pH was adjusted to 6.0 and the bleaching accelerator was added as shown in Table 20 below.

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• 1987
  • 1987-10-06 DE DE8787308819T patent/DE3786895D1/de not_active Expired - Lifetime
  • 1987-10-06 EP EP19870308819 patent/EP0270217B1/fr not_active Expired - Lifetime

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