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
  • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
  • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
  • G03C5/38—Fixing; Developing-fixing; Hardening-fixing
• • 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
  • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
  • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
  • G03C5/264—Supplying of photographic processing chemicals; Preparation or packaging thereof
  • G03C5/265—Supplying of photographic processing chemicals; Preparation or packaging thereof of powders, granulates, tablets

Definitions

• the present invention relates to a solid processing agent for silver halide photographic light-sensitive material (hereinafter also referred to as photographic processing agent), more specifically a solid processing agent for silver halide photographic light-sensitive material capable of fixation which is suitable to the working and social environments in that dust scattering is prevented and no plastic bottles are used.
• photographic processing agent a solid processing agent for silver halide photographic light-sensitive material capable of fixation which is suitable to the working and social environments in that dust scattering is prevented and no plastic bottles are used.
• the black-and-white developer, fixer, color developer, bleacher, bleach-fixer, stabilizer and other processing solutions used to process silver halide photographic light-sensitive material are supplied to the user in the form of one or more dense part solutions contained in plastic bottles for easy handling.
• the user dissolves these processing agent kits in water to prepare starting solutions or replenishers before use.
• mini-labs small photographic processing laboratories using small-sized automatic processing machines, known as mini-labs, have increased rapidly in the field of photographic processing. Accordingly, there has been rapid increase in the consumption of plastic bottles for processing agents.
• plastics In addition to bottles for photographic processing agents, plastics have been widely used for a variety of purposes to make use of their lightness and toughness. The world's annual production of plastics has increased steadily, reaching 100000000 tons in 1988. Meantime, a vast amount of plastics is wasted; for example, about 40% of annual production has been wasted in Japan. Waste plastics deteriorate habitats of marine life when disposed to sea. In Europe, acid rain and other problems arise as a result of incineration of waste plastics in incinerators equipped with poor discharge gas treatment apparatus, provoking major concern.
• a fixer prepared with a stored fixing agent tends to undergo sulfation in a short time, and when used to develop a color light-sensitive material, it tends to cause photographic performance failures such as color image density reduction due to color reproduction failure and increase in the amount of residual silver in the unexposed portion.
• the object of the present invention is to provide a solid processing agent for silver halide photographic light-sensitive material capable of fixation and offering the following features:
• the object of the present invention has been accomplished by a solid processing agent for silver halide photographic light-sensitive material capable of fixation containing at least one kind of thiosulfate wherein the ratio of ammonium cations to the total cation content is not more than 50 mol%.
• the ratio of ammonium cations to the total cation content in the solid processing agent for silver halide photographic light-sensitive material be not more than 20 mol%, since the effect of the invention is enhanced.
• the solid photographic processing agent of the present invention is in a tablet, granule, powder, lump or paste form, with preference given to the tablet form.
• Tablet processing agents can be produced by ordinary methods such as those described in Japanese Patent O.P.I. Publication Nos. 61837/1976, 155038/1979 and 88025/1977 and British Patent No. 1,213,808.
• Granular processing agents can be produced by ordinary methods such as those described in Japanese Patent Application Nos. 109042/1990, 109043/1990, 39735/1991 and 39739/1991.
• Powdery processing agents can be produced by ordinary methods such as those described in Japanese Patent O.P.I. Publication No. 133332/1979, British Patent Nos. 725,892 and 729,862 and German Patent No. 3,733,861.
• the apparent density of the solid processing agent of the present invention is preferably 0.4 to 0.9 g/cm3, in a form of granule, and 1.0 to 5.0 g/cm3 in a tablet form.
• the fixing agents used in the solid photographic processing agent capable of fixation of the present invention are thiosulfate and thiocyanate.
• the amount of thiocyanate added is preferably not less than 0.1 mol/l, more preferably not less than 0.5 mol/l, and still more preferably not less than 1.0 mol/l for processing a color negative film.
• the amount of thiosulfate added is preferably not less than 0.2 mol/l, more preferably not less than 0.5 mol/l for processing a color negative film.
• the object of the present invention can be more efficiently accomplished by using a thiocyanate and a thiosulfate in combination.
• the solid processing agent capable of fixation of the present invention may contain one or more pH regulators comprising various salts. It is also desirable to add a large amount of a re-halogenating agent such as an alkali halide or an ammonium halide, e.g., potassium bromide, sodium bromide, sodium chloride or ammonium bromide.
• a re-halogenating agent such as an alkali halide or an ammonium halide, e.g., potassium bromide, sodium bromide, sodium chloride or ammonium bromide.
• Compounds which are known to be added to fixer or bleach-fixer such as alkylamines and polyethylene oxides, may be added as appropriate.
• a combination of potassium and ammonium salts is preferably selected, and the ratio of ammonium cations to the total cation content in the thiosulfate-containing fixing agent was varied.
• the ratio of ammonium cations to the total cation content in said fixing agent is normally 50 to 0 mol%, preferably 20 to 0 mol%, and more preferably 10 to 0 mol%. Ratios exceeding 50 mol% tend to cause solubility deterioration due to caking, fixer sulfation, color image density reduction upon developing the color light-sensitive material and increase in the amount of residual silver in the unexposed portion.
• Ratios exceeding 50 mol% also considerably deteriorate the strength of tablet photographic processing agent.
• Combined use of thiocyanate enhances the effect of the present invention.
• the ratio of ammonium cations to total cation content is not more than 50 mol%, is defined as a solid processing agent for silver halide photographic light-sensitive material of the present invention, is dissolved in a water in a concentration of prefixed rate.
• a compound represented by the following formula FA specifically one of Example Compounds FA-1 through FA-39, described on page 11 of Japanese Patent Application No. 206120/1990, or a compound in the following group of compounds FB, to the solid photographic processing agent capable of fixation of the present invention, whereby not only the effect of the invention is enhanced but also an additional effect is obtained in that sludge formation in the processing solution capable of fixation is significantly suppressed during prolonged processing of a small amount of light-sensitive material.
• R' and R'' independently represent a hydrogen atom, an alkyl group, an aryl group, an aralkyl group or a nitrogen-containing heterocyclic group; n' represents 2 or 3.
• FB-1 Thiourea
• FB-2 Thiocyanocatechol
• These compounds represented by formula FA and the compounds in the compound group FB may be used singly or in combination.
• Preferred combinations include FB-1 and FA-21, FB-1 and FA-12, FA-12 and FA-38, FA-12 and FA-32, and FA-12 and FA-21.
• FB-1 Greatest preference is given to FB-1.
• a p-phenylenediamine compound having a water-soluble group is preferably used as a color developing agent in the color developer for the present invention, since it enhances the desired effect of the invention and causes little fogging.
• the p-phenylenediamine compounds having a water-soluble group are advantageous over the p-phenylenediamine compounds having no water-soluble group, such as N,N-diethyl-p-phenylenediamine, that they do not contaminate the light-sensitive material and are not irritative to skin upon skin contact.
• the p-phenylenediamine compound for the present invention has at least one water-soluble group as described above on the amino group or benzene nucleus thereof.
• Preferred water-soluble groups include -(CH2) n CH2OH, -(CH2) m NHSO2(CH2) n CH3, -(CH2) m O(CH2) n CH3, -(CH2CH2O) n C m H 2m+1 (m and n independently represent an integer of not less than 0), a -COOH group and a -SO3H group.
• color developing agents preferably used for the present invention are C-1 through C-16 described on pages 26 through 31 of Japanese Patent Application No. 203169/1990, and 4-amino-3-methyl-N-(3-hydroxypropyl)aniline.
• the following compounds Dev-1 through Dev-3 are more preferably used color developing agents.
• the color developing agents described above are used normally in the form of a salt such as hydrochloride, sulfate or p-toluenesulfonate.
• color developing agents may be used singly or in combination, and may be used in combination with black-and-white developing agents such as phenidone, 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrrazolidone and Metol as desired.
• R1 and R2 independently represent an alkyl group, an aryl group, an R3CO- group or a hydrogen atom, provided that R1 and R2 do not represent a hydrogen atom concurrently.
• R1 and R2 may bind together to form a ring.
• the alkyl groups represented by R1 and R2 may be identical or different, each of which preferably has 1 to 3 carbon atoms. These alkyl groups may have a carboxyl group, a phosphate group, a sulfonate group or a hydroxyl group.
• R3 represents an alkoxy group, an alkyl group or an aryl group.
• the alkyl groups and aryl groups for R1, R2 and R3 include those having a substituent.
• R1 and R2 may bind together to form a ring, such as a heterocyclic ring like piperidine, pyridine, triazine or morpholine.
• R11, R12 and R13 independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group
• R14 represents a hydroxyl group, a hydroxyamino group, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a carbamoyl group or an amino group.
• the heterocyclic group is a 5- or 6-membered ring comprising C, H, O, N, S and halogen atoms, whether saturated or unsaturated.
• R14 represents a group selected from an alkyl group, an aryl group and a heterocyclic group; R13 and R14 may cooperate to form a heterocyclic group.
• the alkyl groups, aryl groups and heterocyclic groups represented by R11, R12, R13 and R14 include those having a substituent.
• hydroxylamine compound represented by formula A examples are given in US Patent Nos. 3,287,125, 3,329,034 and 3,287,124 and other publications. Particularly preferable compounds are compound Nos. A-1 through A-39 described on pages 36 through 38 of Japanese Patent Application No. 203169/1990, compound Nos. 1 through 53 described on pages 3 through 6 of Japanese Patent O.P.I. Publication No. 33845/1991 and compound Nos. 1 through 52 described on pages 5 through 7 of Japanese Patent O.P.I. Publication No. 63646/1991.
• Examples of the compound represented by formula B are compound Nos. B-1 through B-33 described on pages 40 through 43 of Japanese Patent Application No. 203169/1990 and compound Nos. 1 through 56 described on pages 4 through 6 of Japanese Patent O.P.I. Publication No. 33846/1991.
• the hydroxylamine compound represented by the following formula A' is also preferably used as a preservative for color developers.
• L represents an alkylene group which may have a substituent
• A represents a carboxyl group, a sulfo group, a phosphono group, a phosphino group, a hydroxyl group, an amino group, ammonium group, carbamoyl group or sulfamoyl group which may have a substituent alkyl group
• R represents a hydrogen atom or an alkyl group which may have a substituent.
• the compound represented by formula A' is exemplified by compound Nos. 1 through 54 described in the lower left column on page 4 through the lower right column on page 6 of Japanese Patent O.P.I. Publication No. 184044/1991, with preference given to the following compounds 1 and 7: 1: HON(CH2COOH)2 7: HON(CH2CH2SO3H)2
• the compound represented by formula A' is prepared by alkylating a commercially available hydroxylamine. It can be synthesized in accordance with the methods described in West German Patent No. 1,159,634 and on pages 101 through 108 of Inorganica Chimica Acta, 93 (1984).
• the color developer used for the present invention may incorporate a trace amount of sulfite as a preservative.
• sulfites include sodium sulfite, potassium sulfite, sodium bisulfite and potassium bisulfite.
• the color developer used for the present invention must contain a buffer.
• buffers include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (boric acid), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate) and potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate).
• Examples of developing accelerators which can be added as necessary include thioether compounds such as those disclosed in Japanese Patent Examined Publication Nos. 16088/1962, 5987/1962, 7826/1963, 12380/1969 and 9019/1970 and US Patent No. 3,813,247, p-phenylenediamine compounds such as those disclosed in Japanese Patent O.P.I. Publication Nos. 49829/1977 and 15554/1975, quaternary ammonium salts such as those disclosed in Japanese Patent Examined Publication No. 30074/1969 and Japanese Patent O.P.I. Publication Nos. 137726/1975, 156826/1981 and 43429/1977, the p-aminophenols disclosed in US Patent Nos.
• chlorine ions and bromine ions may be present in the color developer.
• chlorine ions be contained at 1.0 ⁇ 10 ⁇ 2 to 1.5 ⁇ 10 ⁇ 1 mol, more preferably 3.5 ⁇ 10 ⁇ 2 to 1.0 ⁇ 10 ⁇ 1 mol per liter of color developer.
• Chlorine ion concentrations exceeding 1.5 ⁇ 10 ⁇ 1 mol/l are undesirable for rapidly reaching the maximum density because development is retarded.
• Chlorine ion concentrations of less than 3.5 x 10 ⁇ 2 mol/l are also undesirable because staining occurs and fluctuations in photographic properties (especially minimum density) in continuous processing widen.
• the color developer preferably contains bromine ions at a concentration of 3.0 ⁇ 10 ⁇ 5 to 1.0 ⁇ 10 ⁇ 3 mol/l, more preferably 5.0 ⁇ 10 ⁇ 5 to 5 ⁇ 10 ⁇ 4 mol/l, and still more preferably 1 ⁇ 10 ⁇ 4 to 3 ⁇ 10 ⁇ 4 mol/l.
• Bromine ion concentrations exceeding 1 ⁇ 10 ⁇ 3 mol/l and those lower than 3.0 ⁇ 10 ⁇ 5 mol/l are undesirable because development is retarded and the maximum density and sensitivity lower in the former case and because staining occurs and fluctuations in photographic properties (especially minimum density) occur in continuous processing in the latter case.
• chlorine ions are added directly to the color developer
• examples of chlorine ion sources include sodium chloride, potassium chloride, ammonium chloride, nickel chloride, magnesium chloride, manganese chloride, calcium chloride and cadmium chloride, with preference given to sodium chloride and potassium chloride.
• Chlorine ions may also be supplied in the form of a counterpart salt of the brightening agent added to color developer.
• bromine ion sources include sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, magnesium bromide, manganese bromide, nickel bromide, cadmium bromide, cerium bromide and thallium bromide, with preference given to potassium bromide and sodium bromide.
• the color developer used for the present invention may incorporate antifogging agents which are optionally selected as necessary.
• Antifogging agents which can be used include alkali metal halides such as potassium iodide and organic antifogging agents.
• organic antifogging agents include nitrogen-containing heterocyclic compounds such as benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chlorobenzotriazole, 2-thiazolylbenzimidazole, 2-thiazolylmethylbenzimidazole, indazole, hydroxyazaindolizine and adenine.
• Said brightening agent is preferably represented by the following formula E. wherein X1, X2, Y1 and Y2 independently represent a hydroxyl group, a chlorine atom, a bromine atom or another halogen atom, an alkyl group, an aryl group, or -OR25, wherein R21 and R22 independently represent a hydrogen atom, an alkyl group which may be substituted or an aryl group which may be substituted; R23 and R24 each represent an alkylene group which may be substituted; R25 represents a hydrogen atom, an alkyl group which may be substituted or an aryl group which may be substituted; M represents a cation.
• Example compounds E-1 through E-45 are specified on pages 65 through 67 of the same application, with preference given to E-4, E-24, E-34, E-35, E-36, E-37 and E-41.
• the amount of these compounds added is preferably in the range of 0.2 to 10 g, more preferably 0.4 to 5 g per liter of color developer.
• auxiliary developing agent may be used in combination with the principal developing agent.
• auxiliary developing agents include N-methyl-p-aminophenol hexasulfate (Metol), phenidone, N,N-diethyl-p-aminophenol hydrochloride and N,N,N',N'-tetramethyl-p-phenylenediamine hydrochloride.
• the amount of their addition is preferably 0.01 to 1.0 g/l.
• E represents an alkylene group, a cycloalkylene group, a phenylene group (these three groups may have a substituent), -R5OR5-, -R5OR5OR5- or -R5ZR5-;
• R1 through R5 independently represent an alkylene group which may have a substituent;
• A1 through A5 independently represent a hydrogen atom, a hydroxyl group, a -CO2M group or a -PO3(M)2 group;
• M represents a hydrogen atom or an atom of alkali metal.
• K-2, K-9, K-12, K-13, K-17 and K-19 are preferably used, with greater preference given to K-2 and K-9, which enhances the effect of the present invention when added to the color developer.
• the amount of these chelating agents added is preferably in the range of 0.1 to 20 g, more preferably from 0.2 to 8 g per liter of color developer.
• the color developer may contain a surfactant, whether anionic, cationic, amphoteric or nonionic.
• a surfactant such as alkylsulfonic acid, arylsulfonic acid, aliphatic carboxylic acid and aromatic carboxylic acid may be added as necessary.
• the bleaching agent for the bleacher used for the present invention is a ferric complex salt of organic acid represented by the following formula L. wherein A1 through A4, whether identical or not, independently represent -CH2OH, -COOH or -PO3M1M2 (M, M1 and M2 independently represent a hydrogen atom, an atom of alkali metal or ammonium); X represents an alkylene group having 3 to 6 carbon atoms, which alkylene group may have a substituent.
• Sodium salts, potassium salts and ammonium salts of these ferric complex salts of these compounds L-1 through L-12 can be used optionally, with preference given to ammonium salts of these ferric complex salts from the viewpoint of the desired effect of the present invention and solubility.
• L-1, L-3, L-4, L-5 and L-9 are particularly preferable for the invention, with greater preference given to L-1.
• the bleacher may contain a ferric complex salt of one of the following compounds in addition to an iron complex salts of the compound represented by formula L above as a bleaching agent.
• the amount of ferric complex salt of organic acid added is preferably in the range of 0.1 to 2.0 mol, more preferably 0.15 to 1.5 mol per liter of bleacher.
• Bleaching is accelerated by adding the imidazole derivative described in Japanese Patent O.P.I. Publication No. 295258/1989 or at least one kind of compound represented by formulas I through IX described in the same publication.
• the example compounds described on pages 51 through 115 of Japanese Patent O.P.I. Publication No. 123459/1987, the example compounds described on pages 22 through 25 of Japanese Patent O.P.I. Publication No. 17445/1988 and the compounds described in Japanese Patent O.P.I. Publication Nos. 95630/1978 and 28426/1978 can also be used for the same purpose.
• the bleacher may contain halides such as ammonium bromide, potassium bromide and sodium bromide, various brightening agents, antifoaming agents and surfactants.
• halides such as ammonium bromide, potassium bromide and sodium bromide, various brightening agents, antifoaming agents and surfactants.
• the chelate stability constant is the constant which is well known in "Stability Constants of Metal Ion Complexes", L. G. Sillen and A. E. Martell, The Chemical Society, London (1964), “Organic Sequestering Agents", S. Chaberek and A. E. Martell Wiley (1959) and other publications.
• Examples of chelating agents having a ferric ion chelate stability constant of over 8 include those described in Japanese Patent Application Nos. 234776/1990 and 324507/1989.
• the amount of these chelating agents used is preferably 0.01 to 50 g, more preferably 0.05 to 20 g per liter of stabilizer, in which good results in content range are obtained.
• Ammonium compounds are preferably added to the stabilizer, which are supplied by ammonium salts of various inorganic compounds.
• the amount of ammonium compound added is preferably 0.001 to 2.0 mol, more preferably 0.002 to 1.0 mol per liter of stabilizer. It is also preferable to add a sulfite to the stabilizer.
• the stabilizer preferably contains a metal salt in combination with the chelating agent described above.
• metal salts include salts of Ba, Ca, Ce, Co, In, La, Mn, Ni, Bi, Pb, Sn, Zn, Ti, Zr, Mg, Al and Sr, and it can be supplied as an inorganic salt such as halide, hydroxide, sulfate, carbonate, phosphate or acetate, or a water-soluble chelating agent.
• the amount of its addition is preferably 1 ⁇ 10 ⁇ 4 to 1 ⁇ 10 ⁇ 1 mol, more preferably 4 ⁇ 10 ⁇ 4 to 2 ⁇ 10 ⁇ 2 mol per liter of stabilizer.
• the stabilizer may contain an organic salt such as citrate, acetate, succinate, oxalate or benzoate, and a pH regulator such as malate, borate, hydrochloride or sulfate.
• organic salt such as citrate, acetate, succinate, oxalate or benzoate
• a pH regulator such as malate, borate, hydrochloride or sulfate.
• one or more fungicides can be added, whether singly or in combination, as long as the effect of the invention is not degraded.
• the light-sensitive material to which the processing agent of the present invention is applied is described below.
• a silver iodobromide or silver iodochloride having an average silver iodide content of not less than 3 mol% is used for silver halide grains, with preference given to a silver iodobromide containing 4 to 15 mol% silver iodide.
• the average silver iodide content is preferably 5 to 12 mol%, and ideally 8 to 11 mol%.
• the silver halide emulsions described in Research disclosure No. 308119 (hereinafter referred to as RD308119) can be used.
• the following table shows where the additives are described.
• the silver halide emulsion is used after physical ripening, chemical ripening and spectral sensitization.
• Additives used in these processes are described in Research Disclosure Nos. 17643, 18716 and 308119 (hereinafter referred to as RD17643, RD18716 and RD308119, respectively). The following table shows where the additives are described.
• the light-sensitive material to be processed with the photographic processing agent of the present invention may incorporate various couplers. Examples thereof are described in the above Research Disclosure Numbers. The following table shows where they are described. Item Page in RD308119 RD17643 Yellow coupler 1001, VII-Term D VII-Terms C-G Magenta coupler 1001, VII-Term D VII-Terms C-G Cyan coupler 1001, VII-Term D VII-Terms C-G DIR coupler 1001, VII-Term F VII-Term F BAR coupler 1002, VII-Term F Other couplers which release a useful residue 1001, VII-Term F Alkali-soluble coupler 1001, VII-Term E
• the additives used for the present invention can be added by dispersion as described in RD308119 XIV and by other methods.
• the light-sensitive material may be provided with auxiliary layers such as filter layers and intermediate layers as described in RD308119, VII-Term K.
• auxiliary layers such as filter layers and intermediate layers as described in RD308119, VII-Term K.
• the light-sensitive material of the present invention can have various layer configurations such as the ordinary, reverse and unit structures described in RD308119, VII-Term K.
• silver halide grains based mainly on silver chloride wherein the silver chloride content is at least 80 mol%, more preferably at least 90 mol%, still more preferably at least 95 mol%, and ideally at least 99 mol%.
• Said silver halide emulsion based mainly on silver chloride may contain silver bromide and/or silver iodide in addition to silver chloride in the silver halide composition.
• the silver bromide content is preferably not more than 20 mol%, more preferably not more than 10 mol%, and still more preferably not more than 3 mol%.
• silver iodide When silver iodide is contained, its content is preferably not more than 1 mol%, more preferably not more than 0.5 mol%, and ideally zero.
• Such silver halide grains based mainly on silver chloride having a silver chloride content of not less than 50 mol% are added to at least one silver halide emulsion layer, but it is preferable to add them to all light-sensitive silver halide emulsion layers.
• the crystal configuration of the silver halide grains may be normal crystal, twin crystal or any other crystal, and any ratio of the [1.0.0] plane and the [1.1.1] plane is usable. With respect to the crystal structure of these silver halide grains, it may be uniform from core to outer portion and may be of the core/shell type wherein the core and the outer portion are of different layer (phase) structures. These silver halides may be of the type wherein latent images are formed mainly on the surface or the type wherein latent images are formed mainly inside the grains. Moreover, tabular grains of silver halide such as those described in Japanese Patent O.P.I. Publication No. 113934/1983 and Japanese Patent Application No. 170070/1984 may be used. Also usable are the silver halides described in Japanese Patent O.P.I. Publication Nos. 26837/1989, 26838/1989 and 77047/1989.
• the silver halide grains may be prepared by any of the acid method, neutral method, ammoniacal method and other methods. It is also possible to use the method in which seed grains are formed by the acid method and are grown to a given size by the ammoniacal method, which offers rapid grain growth. In growing silver halide grains, it is preferable to control the pH, pAg and other factors in the reactor and to sequentially and simultaneously add and mix silver ions and halide ions in an amount according to the rate of growth of silver halide grains as described in Japanese Patent O.P.I. Publication No. 48521/1979.
• the silver halide emulsion layer contains color couplers.
• the red-sensitive layer may contain a non-diffusible color coupler which forms a cyan color image, normally a phenol or ⁇ -naphthol coupler.
• the green-sensitive layer may contain at least one non-diffusible color coupler which forms a magenta color image, normally a 5-pyrazolone coupler and or a pyrazolotriazole coupler.
• the blue-sensitive layer may contain at least one non-diffusible color coupler which forms a yellow color image, normally a color coupler having an open chain ketomethylene group. These color couplers may be 6-, 4- or 2-equivalent couplers, for instance.
• a 2-equivalent coupler is particularly preferred for the color light-sensitive material to which the photographic processing agent of the present invention is applied.
• magenta coupler represented by formula M-1 described on page 26 of Japanese Patent O.P.I. Publication No. 106655/1988 (exemplified by Magenta Coupler Nos. 1 through 77 described on pages 29 through 34 of the same publication)
• the cyan coupler represented by formula C-I or C-II described on page 34 of the same publication (exemplified by Cyan Coupler Nos. C'-1 through C'-82 and C''-1 through C''-36 described on pages 37 through 42 of the same publication)
• the rapid yellow coupler described on page 20 of the same publication exemplified by Yellow Coupler Nos. Y'-1 through Y'-39 described on page 21 through 26 of the same publication).
• Sample Nos. 1-1 through 1-16 were prepared with the ratio of ammonium ions to the total cation content in the fixing agent changed by adjusting the ratio of thiosulfate (potassium salt, ammonium salt) and thiocyanate (potassium salt, ammonium salt) as appropriate.
• Each processing agent sample was placed in a polyethylene bag, which was sealed tight, and was stored in an autoclave containing 2.0 kg/cm3 oxygen at 45°C and 65% RH for 1 month. Then, the packing material was cut, and the sample was dissolved in water in a chemical mixer. The caking condition was observed visually.
• a color printing paper sample was prepared as follows:
• Second through seventh layer coating solutions were prepared in the same manner as the first layer coating solution.
• Hardeners H-1 and H-2 were added to layers 2 and 4 and layer 7, respectively.
• Table 1 Layer Composition Amount of addition (g/m2)
• Layer 7 Protective layer Gelatin 1.00
• Layer 6 Ultraviolet absorbing layer Gelatin 0.40 UV absorbent UV-1 0.10 UV absorbent UV-2 0.04 UV absorbent UV-3 0.16
• Layer 5 Red-sensitive layer Gelatin 1.30 Red-sensitive silver chlorobromide emulsion Em-R 0.21* Cyan coupler C-1 0.17 Cyan coupler C-2 0.25 Dye image stabilizer ST-1 0.20
• Layer 4 Ultraviolet absorbing layer Gelatin 0.94 UV absorbent UV-1 0.28 UV absorbent UV-2 0.09 UV absorbent UV-3 0.38 Antistaining
• the mixture was desalinized with a 5% aqueous solution of Demol N, a product of Kao Atlas, and a 20% aqueous solution of magnesium sulfate, and was then mixed with an aqueous solution of gelatin to yield a monodispersed emulsion EMP-1 comprising cubic grains having an average grain size of 0.85 ⁇ m, a coefficient of variance of 0.07 and a silver chloride content of 99.5 mol%.
• the emulsion EMP-1 was chemically ripened with the following compounds at 50°C for 90 minutes to yield a blue-sensitive silver halide emulsion Em-B.
• a monodispersed emulsion EMP-2 comprising cubic grains having an average grain size of 0.43 ⁇ m, a coefficient of variance of 0.08 and a silver chloride content of 99.5 mol% was prepared in the same manner as EMP-1 except that the addition time for Solutions A and B and the addition time for Solutions C and D were changed.
• the emulsion EMP-2 was chemically ripened with the following compounds at 65°C for 120 minutes to yield a green-sensitive silver halide emulsion Em-G.
• Sodium thiosulfate 1.5 mg/mol AgX Chloroauric acid 1.0 mg/mol AgX Stabilizer STAB-1 6 ⁇ 10 ⁇ 4 mol/mol AgX Sensitizing dye GS-1 4 ⁇ 10 ⁇ 4 mol/mol AgX
• a monodispersed emulsion EMP-3 comprising cubic grains having an average grain size of 0.50 ⁇ m, a coefficient of variance of 0.08 and a silver chloride content of 99.5 mol% was prepared in the same manner as EMP-1 except that the addition time for Solutions A and B and the addition time for Solutions C and D were changed.
• the emulsion EMP-3 was chemically ripened with the following compounds at 60°C for 90 minutes to yield a red-sensitive silver halide emulsion Em-R.
• Sodium thiosulfate 1.8 mg/mol AgX Chloroauric acid 2.0 mg/mol AgX Stabilizer STAB-1 6 ⁇ 10 ⁇ 4 mol/mol AgX Sensitizing dye RS-1 4 ⁇ 10 ⁇ 4 mol/mol AgX
• the first and second stabilizing tanks were of the counter current type, and the replenisher was added to the second tank.
• the previously prepared powdery fixing agent sample was dissolved in water, and the resulting processing solution was stored at 38°C for 10 days before use.
• the reflective red color density in the maximum density portion and the amount of residual silver in the exposed portion in the processed color printing paper sample were measured. Also, 1 liter of the fixer tank solution was placed in a beaker with an opening area ratio of 50 cm2/l and stored at 38°C to obtain the number of days required for sulfation.
• Table 3 gives data on the ratio of ammonium cations in the fixer, caking condition, reflective red color density in the maximum density portion, the amount of residual silver in the exposed portion and days required for sulfation.
• the evaluation criteria for caking condition are as follows:
• the ratio (mol%) of ammonium cations in the fixer is preferably not more than 50 mol%, more preferably not more than 20 mol% for the desired effect of the present invention, with better results obtained by using a thiocyanate (potassium salt, ammonium salt) in combination with a thiosulfate (potassium salt, ammonium salt).
• the use of the photographic processing agent of the present invention eliminates the need for conventionally used plastic bottles containing dense solutions of photographic processing agent; plastic consumption decreased by a factor of about 1/5 to 1/30, with the packing material alone needed.
• the processing agent kit volume decreased by a factor of 1/3 to 1/10.
• Example 1 The fixing agent used in Example 1 was granulated in accordance with the method described in Japanese Patent O.P.I Publication No. 109042/1990, using a commercially available fluidized bed spray granulator, to yield a granular processing agent, which was tested in the same manner as in Example 1 and thus found to have improved caking condition, with storage stability (days required for sulfation) improved by 20 to 30%.
• Example 1 The fixing agent mixture used in Example 1 was tableted using a solid processing agent tableting machine made by modifying the Tough Press Correct 1527HU, produced by Kikusui Seisakusho, to yield tablet processing agent sample Nos. 3-1 through 3-16, which were tested in the same manner as in Example 1 and thus found to have improved caking condition, with storage stability (days required for sulfation) improved by 30 to 45%. A tablet strength improving effect was also noted. Data on tablet strength are summarized in Table 4. Tablet strength was evaluated by visual observation after allowing the tablet sample to fall freely from a height of 1.2 m.
• the evaluation criteria for tablet strength are as follows:
• the ammonium cation ratio be not more than 50 mol%, more preferably not more than 20 mol% for sufficient tablet strength.
• the ratio of ammonium ions to the total cation content in the fixing agent was changed as shown in Table 5, by adjusting the ratio of thiosulfate (potassium salt, ammonium salt) and thiocyanate (potassium salt, ammonium salt) as appropriate.
• Figures for the amount of addition in the silver halide photographic light-sensitive material are expressed in grams per m2, unless otherwise stated.
• Figures for silver halide and colloidal silver are expressed as the amount of silver.
• a triacetyl cellulose film support (50 ⁇ m thickness) was subbed on one face (surface), and layers with the following compositions were formed on the opposite face (back face) from the support side.
• Alumina Sol AS-100 (aluminum oxide, produced by Nissan Chemical Industries, Ltd.) 0.8 g
• Diacetyl cellulose 100 mg Stearic acid 10 mg Fine grains of silica (average grain size 0.2 ⁇ m) 50 mg
• Silver iodobromide emulsion having an average grain size of 0.3 ⁇ m 0.40 g
• Sensitizing dye S-1 3.2 ⁇ 10 ⁇ 4 mol/mol silver Sensitizing dye S-2 3.2 ⁇ 10 ⁇ 4 mol/mol silver sensitizing dye S-3 0.2 ⁇ 10 ⁇ 4 mol/mol silver Cyan coupler C-3 0.50 g Cyan coupler C-4 0.13 g
• High boiling solvent Oil-1 0.55 g Gelatin 1.0 g
• Silver iodobromide emulsion having an average grain size of 0.7 ⁇ m 0.90 g Sensitizing dye S-1 1.7 ⁇ 10 ⁇ 4 mol/mol silver Sensitizing dye S-2 1.6 ⁇ 10 ⁇ 4 mol/mol silver Sensitizing dye S-3 0.1 ⁇ 10 ⁇ 4 mol/mol silver Cyan coupler C-4 0.23 g Colored cyan coupler CC-1 0.03 g DIR compound D-2 0.02 g High boiling solvent Oil-1 0.25 g Gelatin 1.0 g
• Silver iodobromide emulsion having an average grain size of 0.4 ⁇ m 0.6 g
• Silver iodobromide emulsion having an average grain size of 0.3 ⁇ m 0.2 g
• Sensitizing dye S-4 6.7 ⁇ 10 ⁇ 4 mol/mol silver Sensitizing dye S-5 0.8 ⁇ 10 ⁇ 4 mol/mol silver Magenta coupler M-2 0.17 g Magenta coupler M-3 0.43 g
• Colored magenta coupler CM-1 0.10 g DIR compound D-3 0.02 g
• High boiling solvent Oil-2 0.7 g Gelatin 1.0 g
• Silver iodobromide emulsion having an average grain size of 0.7 ⁇ m 0.91 g Sensitizing dye S-6 1.1 ⁇ 10 ⁇ 4 mol/mol silver Sensitizing dye S-7 2.0 ⁇ 10 ⁇ 4 mol/mol silver Sensitizing dye S-8 0.3 ⁇ 10 ⁇ 4 mol/mol silver Magenta coupler M-2 0.30 g Magenta coupler M-3 0.13 g Colored magenta coupler CM-1 0.04 g DIR compound D-3 0.004 g High boiling solvent Oil-2 0.35 g Gelatin 1.0 g
• Layer 8 Yellow filter layer YC
• Silver iodobromide emulsion having an average grain size of 0.8 ⁇ m 0.5 g Sensitizing dye S-10 3.0 ⁇ 10 ⁇ 4 mol/mol silver Sensitizing dye S-11 1.2 ⁇ 10 ⁇ 4 mol/mol silver Yellow coupler Y-2 0.18 g Yellow coupler Y-3 0.10 g High boiling solvent Oil-2 0.05 g Gelatin 1.0 g
• Silver iodobromide emulsion having an average grain size of 0.08 ⁇ m 0.3 g UV absorbent UV-4 0.07 g UV absorbent UV-5 0.10 g Additive HS-1 0.2 g Additive HS-2 0.1 g High boiling solvent Oil-1 0.07 g High boiling solvent Oil-3 0.07 g Gelatin 0.8 g
• the color negative film contains compounds SU-1 and SU-4, a viscosity regulator, hardeners H-1 and H-2, a stabilizer STAB-2, antifogging agents AF-1 and AF-2 (weight-average molecular weights of 10000 and 1100000, respectively), dyes AI-4 and AI-5, and compound DI-1 (9.4 mg/m2).
• the silver iodobromide emulsion used in layer 10 was prepared as follows:
• a silver iodobromide emulsion was prepared by the double jet method.
• solutions H-2 and S-2 were added at increasing flow rates (the final flow rate was 5.2 times the initial flow rate) and a pAg of 10.1 and a pH of 6.0 over a period of 60 minutes while keeping a flow rate ratio of 1:1.
• pAg and pH were regulated by the use of an aqueous solution of potassium bromide and a 56% aqueous solution of acetic acid. After grain formation, the mixture was washed by the conventional flocculation method, redispersed in gelatin, and then adjusted to a pH of 5.8 and a pAg of 8.06 at 40°C.
• the resulting emulsion was a monodispersed emulsion comprising octahedral silver iodobromide grains having an average grain size of 0.8 ⁇ m, a distribution width of 12.4% an average silver iodide content of 8.5 mol%.
• Emulsions having different average grain sizes and silver iodide contents were prepared in the same manner as above except that seed crystal average grain size, temperature, pAg, pH, flow rate, addition time and halide composition were changed.
• All these emulsions were core/shell type monodispersed emulsions having a distribution width of not more than 20%. Each emulsion was subjected to optimum chemical sensitization with sodium thiosulfate, chloroauric acid and ammonium thiocyanate, and sensitizing dyes, 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene and 1-phenyl-5-mercaptotetrazole were added.
• the color film sample thus prepared was subjected to exposure through an optical wedge by a conventional method and then processed in the following procedures:
• Color developer (tablet processing agent for 1 liter)
• Fixer tablet processing agent for 1 liter
• the previously prepared tablet fixing agent was dissolved to yield a processing solution, which was stored at 38°C for 10 days before use.
• the transmitted red color density in the maximum density portion (determined using an photoelectric densitometer) and the amount of residual silver in the unexposed portion in the processed sample were measured. Also, 1 liter of the fixer tank solution was placed in a beaker with an opening area ratio of 50 cm2/liter and stored at 38°C to obtain the number of days required for sulfation.
• Table 5 gives data on the ratio of ammonium cations in the fixer, caking condition, transmitted red color density in the maximum density portion, the amount of residual silver in the exposed portion, days until sulfation and tablet strength.
• sample Nos. 4-1 through 4-14 all of which were prepared in accordance with the present invention and wherein the ammonium cation ratio (mol%) in the fixer was not more than 50 mol%, are better than comparative samples with respect to all items, with still better results obtained from sample Nos. 4-1 through 4-11, wherein the ratio was not more than 20 mol%.
• Sample Nos. 4-4 through 4-8, incorporating a thiocyanate (potassium salt, ammonium salt) also gave excellent results.
• the present invention provides a solid processing agent for silver halide photographic light-sensitive material capable of fixation which has improved storage stability, improved solubility and increased wear resistance and which is free of color image density reduction after development.

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• 1991
  • 1991-12-13 JP JP3330735A patent/JP3038418B2/ja not_active Expired - Fee Related
• 1992
  • 1992-12-07 EP EP92311116A patent/EP0546778A1/fr not_active Withdrawn

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