EP0426193B1 - Photographisches Silberhalogenidmaterial, Verarbeitungslösung und dessen Verarbeitungsverfahren - Google Patents

Photographisches Silberhalogenidmaterial, Verarbeitungslösung und dessen Verarbeitungsverfahren Download PDF

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Publication number
EP0426193B1
EP0426193B1 EP90121044A EP90121044A EP0426193B1 EP 0426193 B1 EP0426193 B1 EP 0426193B1 EP 90121044 A EP90121044 A EP 90121044A EP 90121044 A EP90121044 A EP 90121044A EP 0426193 B1 EP0426193 B1 EP 0426193B1
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Prior art keywords
ring
group
processing
solution
photographic material
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EP90121044A
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English (en)
French (fr)
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EP0426193A1 (de
Inventor
Junji C/O Fuji Photo Film Co. Ltd. Nishigaki
Akihiko C/O Fuji Photo Film Co. Ltd. Ikegawa
Masaki C/O Fuji Photo Film Co. Ltd. Okazaki
Minoru C/O Fuji Photo Film Co. Ltd. Yamada
Nobuhiko C/O Fuji Photo Film Co. Ltd. Uchino
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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Priority claimed from JP1286660A external-priority patent/JP2632055B2/ja
Priority claimed from JP1289312A external-priority patent/JP2579223B2/ja
Application filed by Fuji Photo Film Co Ltd filed Critical Fuji Photo Film Co Ltd
Publication of EP0426193A1 publication Critical patent/EP0426193A1/de
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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
    • 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
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • 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
    • 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
    • G03C7/392—Additives
    • G03C7/39208—Organic compounds
    • G03C7/3924—Heterocyclic
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/407—Development processes or agents therefor

Definitions

  • the present invention relates to a process for the processing of a silver halide photographic material. More particularly, the present invention relates to a process for the processing of a silver halide photographic material which provides improvements in photographic properties and which provides improved ability to inhibit residual coloration.
  • rapid development processing has the advantage that with more rapid development processing, smaller tank capacities are required to develop a unit quantity of photographic material in a unit time, and hence a smaller automatic processor may be employed. Rapid development processing is therefore of great importance.
  • sensitizing dyes contained in silver halide photographic materials do not elute during processing, leaving the inside of the photographic materials discolored (so-called residual coloration) or a problem occurs in that sensitizing dyes are delayed in desorption from silver halide grains, deteriorating photographic properties (e.g., inhibition of development, fixation and bleach).
  • JP-A-64-4739, JP-A-64-15734, JP-A-1-9451, JP-A-1-35440, JP-A-1-21444, JP-A-1-35441, and JP-A-1-159645 are effective. However, these methods do not necessarily provide satisfactory results.
  • EP-A-0 413 314 which is state of the art under the provisions of Art. 54(3) EPC describes a silver halide photographic material having improved residual coloration and fixing properties wherein the following compounds may be contained:
  • an object of the present invention is to provide a process for rapid development processing.
  • a further object of the present invention is to provide a process for the processing of a silver halide photographic material which overcomes the problem of residual coloration which is caused by non-eluted sensitizing dyes which may remain after rapid processing or the problem of deterioration in the photographic properties.
  • Yet a still further object of the present invention is to provide a process for the processing of a silver halide photographic material which has excellent preservability and adaptability to running processing.
  • a method for the processing of a silver halide photographic material comprising processing a spectrally sensitized silver halide photographic material with a processing solution containing a compound represented by the general formula (I) or (II) or a salt thereof; wherein Z 1 represents a nonmetallic atom group required to form an unsaturated ring; Y 1 represents an oxygen atom, a sulfur atom or in which R 11 represents a hydrogen atom or an alkyl group; R 1 represents an alkyl group substituted with an amino, dialkylamino or sulfonamido group; and X 1 represents an oxygen atom wherein Z 2 represents a nonmetallic atom group required to form an unsaturated ring; Y 2 represents an oxygen atom, a sulfur atom or in which R 12 has the same meaning as R 11 ; R 2 represents an alkyl group substituted with an amino group, a dialkylamino group or a sulfonamido group;
  • Preferred examples of the unsaturated rings formed by Z 1 or Z 2 include monocyclic and polycyclic unsaturated carbocyclic and heterocyclic rings such as a benzene ring, a naphthalene ring, and a 5- or 6-membered heterocyclic ring. These rings may contain substituents. Specific examples of suitable substituents are the same as defined later for Z.
  • these 5- or 6-membered heterocyclic rings are a pyridine ring, a pyrimidine ring, a pyrazine ring, a furan ring, a thiene ring, a pyrrole ring, a triazine ring, an imidazole ring, a quinazoline ring, a purine ring, a quinoline ring, an acridine ring, an indole ring, a thiazole ring, an oxazole ring, a selenazole ring, a furazalane ring, and a heterocyclic ring in which these heterocyclic rings are further condensed with a benzo condensed ring or a naphtho condensed ring or to each other.
  • the alkyl group represented by R 11 , R 12 or R 22 may contain substituents. These groups (including a substituent) each preferably contains 10 or less carbon atoms. Preferred examples of such substituents include an amino group, an ammonio group, a hydroxyl group, a carboxyl group, a sulfo group, a phosphonic acid, a sulfonyl group, a sulfonamido group, an amide group, an acyl group, a cyano group, an alkoxycarbonyl group, an aryloxycarbonyl group, a ureide group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a nitrogen-containing heterocyclic residue, an alkyl group, and an aryl group. These substituents may be further substituted.
  • R 1 and R 2 represent an alkyl group substituted by an amino group, a dialkylamino group or a sulfonamido group. Particularly preferred of these alkyl groups is an alkyl group substituted by a dialkylamino group.
  • R 11 and R 12 include an alkyl group substituted by a dialkylamino group, an unsubstituted alkyl group, and an alkoxy group.
  • Preferred examples of R 22 include a hydrogen atom.
  • Y 1 is a sulfur atom
  • X 1 is an oxygen atom
  • Preferred of the groups represented by X 2 is -O- or -NH-.
  • Preferred of the unsaturated rings formed by Z are a benzene ring, a naphthalene ring, and a 5- or 6-membered heterocyclic ring.
  • Preferred examples of such 5- or 6-membered heterocyclic ring include a pyridine ring, a pyrimidine ring, a pyrazine ring, a furan ring, a thiene ring, a pyrrole ring, a triazine ring, an imidazole ring, a quinazoline ring, a purine ring, a quinoline ring, an acridine ring, an indole ring, a thiazole ring, an oxazole ring, a selenazole ring, a furazalane ring, and a heterocyclic ring in which these heterocyclic rings are condensed with a benzo condensed ring or a naphtho condensed ring or to
  • the rings represented by Z include those containing substituents.
  • suitable substituents include a hydroxyl group, an alkoxy group, an aryloxy group, a carboxyl group, an amino group, an ammonio group, a sulfo group, a phosphonic acid group, a sulfonyl group, a ureide group, an acyl group, an alkylthio group, an arylthio group, a carbamoyl group, a sulfamoyl group, an acylamino group, a sulfonamido group, an oxo group, a halogen group, a cyano group, a nitro group, an alkyl group, an alkenyl group, an alkynyl group, and an aryl group. These groups may contain substituents.
  • R represents an alkyl group substituted with a sulfo group, a dialkylamino group or a phosphonic acid group (preferably an alkyl group containing 4 or less carbon atoms, e.g., methyl, ethyl, propyl), an aryl group (preferably an aryl group containing a benzene nucleus, e.g., phenyl), an acyl group (preferably an acyl group containing 10 or less carbon atoms, e.g., acetyl, benzoyl), an allyl group, or an alkanesulfonyl group (preferably an alkanesulfonyl group containing 3 or less carbon atoms, e.g., methanesulfonyl, ethanesulfonyl, propanesulfonyl).
  • a sulfo group preferably an alkyl group containing 4 or less carbon atoms, e.g.,
  • Examples of the aryl group, acyl group, alkanesulfonyl group represented by R include those containing substituents.
  • substituents include a hydroxyl group, an alkoxy group, an aryloxy group, a carboxyl group, an amino group, an ammonio group (examples of amino groups and ammonio groups include those containing substituents; two or more such substituents may be connected to each other to form a ring such as a morpholino ring), a sulfo group, a phosphono group, a sulfonyl group, a ureide group, an acyl group, an alkylthio group, an arylthio group, a carbamoyl group, a sulfamoyl group (examples of carbamoyl groups and sulfamoyl groups include those containing substituents; two or more such substituents may be connected to each other to form a ring such
  • a carboxyl group, a sulfo group, and a phosphono group may be in the form of salt with an alkali metal (e.g., sodium, potassium) or monovalent positive atom (e.g., NH 4 + ).
  • the amino group may form a salt with various acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, oxalic acid and acetic acid.
  • Particularly preferred examples of R include an alkyl group substituted with a dialkylamino group, a sulfonic acid group, and a phosphonic acid group.
  • the compound represented by the general formula (I), (II) or (III) preferably has a molecular weight of 600 or less, more preferably 500 or less.
  • the compound represented by the general formula (I), (II) or (III) is preferably water-soluble. Such a compound is preferably soluble in water in a proportion of 0.04 g or more, particularly 0.08 g or more, per 100 cc of water at a temperature of 20°C.
  • the compound represented by the general formula (I) or (II) may be used in the form of a salt with an inorganic or organic acid.
  • inorganic or organic acids include hydrochloric acid, sulfuric acid, nitric acid, hydrobromic acid, hydroiodic acid, perchloric acid, oxalic acid, p-toluenesulfonic acid, methanesulfonic acid, and trifluoromethanesulfonic acid.
  • the compound represented by the general formula (III) may be in the form of tautomeric enol.
  • JP-B-54-18338 Journal of Organic Chemistry , vol. 24, page 1478 (1959), Journal of Chemical Society , page 442, 1957, and Journal of Heterocyclic Chemistry , vol. 22, page 313 and page 1065, 1985, or by methods analogous thereto.
  • JP-B as used herein means an "examined Japanese patent publication”.
  • the compounds of the general formula (I), (II) or (III) used in the present invention serve to enable rapid processing of a silver halide photographic material.
  • the present compounds serve to extremely minimize the amount of sensitizing dye left in the photographic material which has been processed.
  • the compound of the general formula (I), (II), or (III) is incorporated in the processing solution.
  • the photographic processing of the present invention in the case of a black-and-white light-sensitive material, comprises at least the steps of developing, fixing, rinsing (or stabilizing) and drying the silver halide photographic material which has been exposed to light.
  • the present photographic processing comprises at least the steps of color-developing, bleaching, fixing (bleach and fixation may be effected in the same bath, i.e., a blix bath), rinsing (or stabilizing), and drying the silver halide photographic material which has been exposed to light.
  • the compound of the general formula (I), (II), or (III) may be incorporated in any of a developer, color developer, fixing solution, bleaching solution, blix solution, rinsing solution, and prebath thereof.
  • the compound is preferably incorporated in a developer, a color developer, a fixing solution, a blix solution, a rinsing solution or a prebath thereof.
  • the processing solution used in the present invention is a developer, a color developer, a fixing solution, a bleaching solution, a blix solution or a prebath thereof containing a compound represented by the general formula (I), (II), or (III).
  • the amount of the compound of the general formula (I), (II), or (III) to be incorporated in the processing solution depends on the kind of processing solution but is generally in the range of 5 ⁇ 10 -5 to 10 -1 mol/l, preferably 10 -4 to 5 ⁇ 10 2 mol/l, particularly 3 ⁇ 10 -2 to 10 -2 mol/l. If this amount falls below this range, the effect of improving adaptability to rapid processing cannot be obtained. On the contrary, if the amount exceeds this range, precipitation in the processing solution occurs or the manufacturing cost is increased.
  • the silver halide photographic material used in the present invention exhibits pronounced effects when a silver halide photographic material which has been spectrally sensitized is processed rapidly, preferably for 90 seconds or less, particularly 70 seconds or less.
  • the silver halide photographic material used in the present invention is a black-and-white photographic material, it is most preferably developed with a developer containing a combination of a dihydroxybenzene and a 1-phenyl-3-pyrazolidone. Other p-aminophenol-based developing agents may also be included, if desired.
  • dihydroxybenzene developing agents examples include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,3-dibromohydroquinone, and 2,5-dimethylhydroquinone. Particularly preferred of these dihydroxybenzene developing agents is hydroquinone.
  • p-aminophenol-based developing agents examples include N-methyl-p-aminophenol, p-aminophenol, N-( ⁇ -hydroxyethyl)-p-aminophenol, N-(4-hydroxyphenyl)glycine, 2-methyl-p-aminophenol, and p-benzylaminophenol. Particularly preferred of these p-aminophenol-based developing agents is N-methyl-p-aminophenol.
  • 3-pyrazolidone-based developing agents examples include l-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1-p-aminophenyl-4,4-dimethyl-3-pyrazolidone, 1-p-tolyl-4,4-dimethyl-3-pyrazolidone, and 1-p-tolyl-4-methyl-4-hydroxymethyl-3-pyrazolidone.
  • the developing agent is preferably used in an amount of 0.01 to 1.2 mol/l.
  • sulfite preservatives used in the processing solution include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, and potassium metabisulfite.
  • the sulfites are preferably used at 0.2 mol/l or more, particularly 0.4 mol/l. Furthermore, an upper limit of 2.5 mol/l is preferred.
  • the pH of the developer is preferably in the range of 9 to 13, more preferably 10 to 12.
  • alkalis to be used to set the pH examples include pH adjusters such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium triphosphate, and potassium triphosphate.
  • Buffers such as those described in JP-A-62-186259 (borates), those described in JP-A-60-93433 (e.g., saccharose, acetoxime, 5-sulfosalicylic acid), phosphates, and carbonates may also be used.
  • Film hardeners may also be incorporated in the above mentioned developer.
  • film hardeners preferably used are dialdehyde-based film hardeners or bisulfite addition products thereof.
  • Specific examples of these film hardeners include glutaraldehyde, and bisulfite addition products thereof.
  • additives which may be used in addition to the above-mentioned constituents include development inhibitors such as sodium bromide, potassium bromide and potassium iodide; organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve, hexylene glycol, ethanol and methanol; and antifoggants such as 1-phenyl-5-mercaptotetrazole, sodium 2-mercaptobenzimidazole-5-sulfonate, and other mercapto compounds, 5-nitroindazole and other indazole-based compounds, and 5-methylbenzotriazole and other benzotriazole-based compounds.
  • development inhibitors such as sodium bromide, potassium bromide and potassium iodide
  • organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve, hexylene glycol, ethanol and methanol
  • antifoggants such as 1-phen
  • additives which may be used include development accelerators as described in Research Disclosure , No. 17643, vol. 176, Section XXI (December 1978). If desired, toners, surface active agents, defoaming agents, water softeners, and amino compounds as described in JP-A-56-106244 can also be present.
  • Silver stain inhibitors such as the compounds as described in JP-A-56-24347 can be incorporated in the developer in the development processing.
  • the developer can comprise amino compounds such as the alkanolamines described in EP-B- 0,136,582 and JP-A-56-106244.
  • the developer can also comprise those compounds described in L.F.A. Mason, Photographic Processing Chemistry , pp. 226-229, Focal Press, 1966, US-A- 2,193,015 and US-A- 2,592,364, and JP-A-48-64933.
  • the fixing solution to be used in the present invention is an aqueous solution containing a thiosulfate as a fixing agent and a pH of 3.8 or more, more preferably 4.2 to 7.0, and most preferably 4.5 to 5.5.
  • suitable fixing agents include sodium thiosulfate, and ammonium thiosulfate. Particularly preferred of these fixing agents is ammonium thiosulfate from the standpoint of fixing speed.
  • the amount of fixing agent to be used can be appropriately varied, but is generally in the range of about 0.1 mol/l to about 6 mol/l.
  • the fixing solution can comprise a water-soluble aluminum salt which serves as a film hardener.
  • water-soluble aluminum salts include aluminum chloride, aluminum sulfate, and potash alum.
  • the fixing solution can comprise tartaric acid, citric acid, gluconic acid, and derivatives thereof, alone or in combination. These compounds are effective if present in a concentration of 0.005 mol or more, particularly 0.01 to 0.03 mol, per 1 of fixing solution.
  • the fixing solution can comprise preservatives (e.g., sulfite, bisulfite), pH buffers (e.g., acetic acid, boric acid), pH adjusters (e.g., sulfuric acid), chelating agents capable of softening water, and the compounds as described in JP-A-62-78551.
  • preservatives e.g., sulfite, bisulfite
  • pH buffers e.g., acetic acid, boric acid
  • pH adjusters e.g., sulfuric acid
  • the processing hardening by reducing the percentage swelling of the photographic material (preferably 150% to 50%) since this facilitates faster processing.
  • the hardening reaction may also be reduced by adopting a pH of 4.6 or more in the fixing solution.
  • a replenishing agent composed of a developing solution and a fixing solution respectively in a single solution, which has the advantage that a simple dilution with water is sufficient for adjusting the replenishment solution.
  • the above-mentioned silver halide photographic materials used in the present invention are processed with washing water or a stabilizing solution after the developing and fixing stages.
  • the stabilizing solution is the same as for the washing, the nomenclature being all that is different.
  • the replenishment rate of the washing water or stabilizing solution is preferably in the range of 2 l or less (including 0, which is to say a standing water wash) per m 2 of photographic material.
  • a known approach for reducing the replenishment rate is the multi-stage countercurrent system (for example with 2 or 3 stages). If a multi-stage counter-current system is applied in the present invention, even more efficient washing can be attained, since, after the material has been fixed, the photographic material progressively contacts a gradually cleaner washing solution, which is to say in the direction of the processing solution which is not contaminated by the fixing solution.
  • Suitable antimicrobial means include use of the ultraviolet irradiation method described in JP-A-60-263939, the method using a magnetic field described in JP-A-60-263940, the method in which water is purified using an ion-exchange resin described in JP-A-61-131632, and methods using antibacterial agents described in JP-A-62-115154, JP-A-62-153952, JP-A-62-220951, and JP-A-62-209532.
  • antibacterial agents antifungal agents and surface active agents as described in L.E. West, “Water Quality Criteria”, Photo. Sci. & Eng. , vol. 9, No. 6 (1965), M.W. Beach, “Microbiological Growths in Motion-Picture Processing", SMPTE Journal, vol. 85, 1976, R.O. Deegan, "Photo Processing Wash Water Biocides”, J. Imaging Tech 10, No. 6 (1984), and JP-A-57-8542, 57-58143, 58-105145, 57-132146, 58-18631, 57-97530, and 57-157244.
  • washing bath and stabilizing bath can comprise isothiazoline-based compounds as described in R.T. Kreiman, J. Image. Tech. 10 , (6), page 242, 1984, and Research Disclosure Nos. 20526, vol. 205, May 1981, and 22845, vol. 228, April 1983, and compounds as described in JP-A-62-209532 as microbiocides.
  • part or all of the overflow from the washing or stabilization bath which is produced by replenishing the washing or stabilization bath with water which has undergone an antifungal stage in the processing, can be used in a processing solution having a fixing capability, which is the preceding processing stage, as described in JP-A-60-235133.
  • the silver halide photographic material used in the present invention is a black-and-white material, and when it is processed in an automatic processor including at least the above developing, fixing and washing or stabilizing and drying steps, it is preferable that the steps from development to drying be completed within 90 seconds, which is to say that the time taken from when the front edge of the photographic material is immersed in the developing solution, as it passes through the fixing and washing (or stabilization) stages and is dried and until the front edge emerges from the drying zone (the so-called dry to dry time) is 90 seconds or less, and this is particularly preferably 70 seconds or less. More preferably, this dry to dry time is 60 seconds or less.
  • the time taken in the developing step or the “developing time” refers to the time from when the front end of the photographic material being processed is immersed in the solution in the developing tank in an automatic processor until it is immersed in the fixing solution which follows
  • the "fixing time” refers to the time from when it is immersed in the solution in the fixing tank until it is immersed in the washing tank solution (stabilizing solution) which follows
  • the “washing time” refers to the time during which it is immersed in the washing tank solution.
  • an automatic processor is normally equipped with a drying zone through which a hot gas of 35°C to 100°C, and preferably 40°C to 80°C, is passed and the "drying time" refers to the time spent in this drying zone.
  • the developing time is 30 seconds or less and preferably 25 seconds or less
  • the developing temperature is preferably in the range of 25°C to 50°C, more preferably 30°C to 40°C.
  • the fixing temperature and time in the present invention are preferably in the range of about 20°C to about 50°C and 6 seconds to 30 seconds, more preferably 30°C to 40°C and 6 seconds to 20 seconds, respectively.
  • the washing or stabilization temperature and time are preferably in the range of 0 to 50°C and 6 seconds to 20 seconds, more preferably 15°C to 40°C and 6 seconds to 15 seconds, respectively.
  • the photographic material which has been developed, fixed and washed or stabilized is dried by pressing out the washing water, for example, by passing it through squeeze rollers. Drying is at about 40°C to about 100°C and the drying time may be varied depending to the surrounding conditions, but it is normally about 5 seconds to 30 seconds, more preferably 40°C to 80°C for about 5 seconds to 20 seconds.
  • the structure of the rollers in the fixing solution tank results in a more rapid fixing rate and involves facing rollers.
  • the photographic material used in the present invention can be a scanner material for printing or a photographic material for laser printers in medical imaging, or a direct X-ray material for medical purposes, an indirect X-ray material for medical purposes, a CRT image-recording material, a high-contrast material, a color reversal material, a color printing paper and the like.
  • the production of the photographic material used in the present invention can be carried out, for example, by one or a combination of two or more of the following methods.
  • the silver halide grains in the photographic emulsion may be the so-called regular grains having a cubic, octahedral, tetradecahedral or other such regular crystal form, or those having a spherical or other such irregular crystal form, those having twin crystal surfaces or other such crystal defects, or they may be tabular grains or complex forms of these, with tabular grains being preferable.
  • the aspect ratio of the tabular grains is given as the ratio between the average value of the diameters of circles having the same surface area as the projected surface area of each of the tabular grains and the average value of the grain thickness of each of the tabular grains.
  • preferred tabular grains have aspect ratio of 4 or more and under 20 and more preferably 5 or more and under 10.
  • the grain thickness is preferably 0.3 ⁇ m or less and particularly preferably 0.2 ⁇ m or less.
  • 80% by weight, and more preferably 90% by weight or more, of all the grains be tabular grains.
  • a monodisperse emulsion in which the silver halide grain size has a narrow distribution or a polydisperse emulsion which has a wide distribution may be employed.
  • the preparation of the silver halide photographic emulsion used in the present invention can be accomplished by any suitable known method as described in Research Disclosure , No. 17643, December 1978, pp. 22-23, "I. Emulsion Preparation and Types", and Research Disclosure , No. 18716 (November 1979), page 648.
  • the preparation of the photographic emulsion to be used in the present invention also can be accomplished by any suitable method as described in described in P. Glafkides, Chimie et Phisique Photographique , Paul Montel, 1967, G.F. Duffin, Photographic Emulsion Chemistry , Focal Press, 1966, and V.L. Zelikman et al, Making and Coating Photographic Emulsion , Focal Press, 1964.
  • silver halide solvents ammonia, potassium thiocyanate, ammonium thiocyanate, the thioether compounds as described in US-A- 3,271,157, US-A- 3,574,628, US-A- 3,704,130, US-A- 4,297,439, and US-A- 4,276,374, the thione compounds as described in JP-A-54-144319, JP-A-53-82408, and JP-A-55-777737, and the amine compounds as described in JP-A-54-100717.
  • water-soluble rhodium salts and water-soluble iridium salts mentioned above can be used.
  • the one-sided mixing method, the simultaneous mixing method, a combination thereof and the like may all be used as the system for reacting soluble silver salts and soluble halogen salts.
  • One form of the simultaneous mixing method is a method in which the pAg is kept constant in the liquid phase in which the silver halide is formed, in other words, the controlled double jet method, and this method provides silver halide grains with a regular grain form and a nearly uniform grain size.
  • the silver halide emulsion to be used in the present invention is preferably subjected to chemical sensitization.
  • Chemical sensitization can be in the usual manner and sulfur sensitization, reduction sensitization, noble metal sensitization and combinations thereof may be used for chemical sensitization.
  • chemical sensitizers include sulfur sensitizers such as allyl thiocarbamides, thioureas, thiosulfates, thioethers and cystines; noble metal sensitizers such as potassium chloroaurate, aurous thiosulfate and potassium chloropalladate; and reducing sensitizers such as tin chloride, phenyl hydrazine and redactone.
  • sulfur sensitizers such as allyl thiocarbamides, thioureas, thiosulfates, thioethers and cystines
  • noble metal sensitizers such as potassium chloroaurate, aurous thiosulfate and potassium chloropalladate
  • reducing sensitizers such as tin chloride, phenyl hydrazine and redactone.
  • the silver halide emulsion used in the present invention can be spectrally sensitized with known spectral sensitizing dyes as desired.
  • spectral sensitizing dyes which may be used include the cyanine, merocyanine, rhodacyanine, styryl hemicyanine, oxonol, benzylidene and holopolar sensitizing dyes as described in F.M. Hamer, Heterocyclic Compounds - The Cyanine Dyes and Related Compounds, John Wiley & Sons, 1964, and D.M. Sturmer, Heterocyclic Compounds - Special Topics in Heterocyclic Chemistry, John Wiley & Sons, 1977.
  • Particularly preferred of these sensitizing dyes are cyanine and merocyanine dyes, most preferably benzoimidazolobenzoxazolocarbocyanine dyes.
  • sensitizing dyes which can be preferably used in the present invention include cyanine dyes and merocyanine dyes as described in JP-A-60-133442, JP-A-61-75339, JP-A-62-6251, JP-A-59-212827, JP-A-50-122928, and JP-A-59-1801553.
  • Specific examples of these sensitizing dyes include sensitizing dyes which spectrally sensitize silver halides in the blue region, green region, red region or infrared region of the spectrum as described in JP-A-60-133442 (pp. 8-11), JP-A-61-75339 (pp. 5-7 and 24-25), JP-A-62-6251 (pp. 10-15), JP-A-59-212827 (pp. 5-7), JP-A-50-122928 (pp. 7-9), and JP-A-59-180553 (pp. 7-18).
  • sensitizing dyes can be used alone or in combination: Combinations of sensitizing dyes are often used for the purpose of supersensitization in particular. Dyes which do not themselves provide a spectral sensitizing action and substances exhibiting a supersensitizing effect, which are substances which essentially do not absorb visible light, may be included in the emulsion together with the sensitizing dyes.
  • substituted aminostilbene compounds which are nitrogen-containing heterocyclic nuclei (for example those described in US-A- 2,933,390 and US-A- 3,635,721), aromatic organic acid formaldehyde condensates (for example those described in US-A- 3,743,510), cadmium salts and azaindene compounds.
  • substituted aminostilbene compounds which are nitrogen-containing heterocyclic nuclei (for example those described in US-A- 2,933,390 and US-A- 3,635,721), aromatic organic acid formaldehyde condensates (for example those described in US-A- 3,743,510
  • sensitizing dyes are incorporated in the silver halide photographic emulsion in a proportion of 5 ⁇ 10 -7 to 5 ⁇ 10 -2 mol, preferably 1 ⁇ 10 -6 to 1 ⁇ 10 -3 mol, particularly 2 ⁇ 10 -6 to 5 ⁇ 10 -4 mol per mol of silver halide.
  • sensitizing dyes can be directly dispersed into the emulsion layer. Furthermore, these dyes may be first dissolved in a suitable solvent such as methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, water, pyridine and a mixture thereof, and added to the emulsion in the form of a solution. Further, ultrasonic waves can be used to produce the solution.
  • a suitable solvent such as methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, water, pyridine and a mixture thereof.
  • the method of addition of the above mentioned sensitizing dyes can be the method in which the dye is dissolved in a volatile organic solvent, the resulting solution is dispersed in a hydrophilic colloid and this dispersion is added to the emulsion as described in US-A- 3,469,987; the method in which a water-insoluble dye is dispersed in a water-soluble solvent without being dissolved and this dispersion is added to the emulsion as described in JP-B-46-24185; the method in which a water-insoluble dye is mechanically crushed and dispersed in a water-based solvent and this dispersion is added to the emulsion as described in JP-B-61-45217; the method in which the dye is dissolved in a surface active agent and the resulting solution is added to the emulsion as described in US-A- 3,822,135; the method in which the dye is dissolved using a red-shifting compound and the resulting solution is added to the emulsion as described in JP-
  • the methods as described in US-A- 2,912,343, US-A- 3,342,605, US-A- 2,996,287, and US-A- 3,429,835 can also be used for the addition of the dye to the emulsion.
  • the above sensitizing dyes may be dispersed uniformly in the silver halide emulsion before it is coated onto an appropriate support, and the dyes can also be dispersed at any stage in the preparation of the silver halide emulsion.
  • sensitizing dyes can be used in combination with the above sensitizing dyes.
  • the percentage swelling of the silver halide photographic material is preferable to keep the percentage swelling of the silver halide photographic material at 200% or less.
  • the percentage swelling is no lower than required since if it is too low, there is a reduction in the rapidity of development, fixing, washing and the like.
  • the preferred percentage swelling is between 200% and 30%, particularly between 150% and 50%.
  • the percentage swelling can be determined by (a) incubating the photographic material for 3 days at 38°C and 50% RH, (b) measuring the thickness of the hydrophilic colloid layer, (c) immersing the photographic material in distilled water at 21°C, and (d) comparing the thickness of the hydrophilic colloid layer with that measured in step (b).
  • Known film hardeners which can be used for the photographic materials in the present invention include aldehyde compounds, compounds having active halogens as described in US-A- 3,288,775, compounds having a reactive ethylenically unsaturated group as described in US-A- 3,635,718, epoxy compounds as described in US-A- 3,091,537, halocarboxaldehydes such as mucochloric acid and other such organic compounds.
  • vinyl sulfone-based film hardeners are preferred.
  • macromolecular film hardeners are also preferred.
  • Polymers having an active vinyl group or a group comprising a precursor thereof are preferred as macromolecular film hardeners, and of these, particular preference is given to polymers of the kind in which the active vinyl group or the group constituting a precursor thereof is joined to the main polymer chain via a long spacer as described in JP-A-56-142524.
  • the amount of these film hardeners to be incorporated to achieve the percentage swelling discussed above will vary depending on the type of film hardener and the type of gelatin used.
  • the silver halide photographic material used in the present invention is processed rapidly, it is preferable to include an organic substance of a type which flows out in the development processing stage from the emulsion layers and/or other hydrophilic colloid layers.
  • the substance which flows out is gelatin
  • hydrophilic polymers such as polyacrylamide as described in US-A- 3,271,158 or polyvinyl alcohol and the like can be used to advantage as macromolecular substances.
  • Dextran and saccharose, pullulan and other such saccharides are also advantageous.
  • polyacrylamide and dextran are preferred, and polyacrylamide is a particularly preferred substance.
  • the average molecular weight of these substances is preferably in the range of 20,000 or less, more preferably 10,000 or less.
  • stabilizers and antifoggants as described in Research Disclosure , No. 17643, vol. 176, Section VI (December 1978).
  • the silver halide photographic materials used in the present invention can be put to use as silver halide photographic materials capable of providing photographic characteristics of high speed and ultrahigh contrast by the use of a hydrazine derivative as described in US-A- 4,224,401, US-A- 4,168,977, US-A- 4,166,742, US-A- 4,311,781, US-A- 4,272,606, US-A- 4,221,857, and US-A- 4,243,739.
  • present invention can also be used for silver halide color photographic materials.
  • the use of the present invention for silver halide color photographic materials is discussed in detail below.
  • the first stage in the processing of a color photographic material designates the processing stage which is carried out initially, and this normally corresponds to color development in the processing of color negative films.
  • the so-called wet processing time which is the time from when the photographic material is immersed in the processing solution of the first stage until it leaves the processing solution of the final stage, is 6 minutes or less
  • the present invention has a good effect, and the effect is more pronounced when this time is reduced to 5 minutes 30 seconds or less, which is therefore preferred, 5 minutes or less being even more preferred.
  • the fixing or bleach-fixing time is 2 minutes or less and, when this is reduced to 1 minute 30 seconds or less this is even more preferred from the standpoint of the clarity of the effect.
  • the present invention can be appropriately used when the total replenishment amount for each of the processing solutions is 2,500 ml or less and, preferably 2,000 ml or less, with 1,800 ml or less, per m 2 of color photographic material, being even more preferred.
  • a replenishment rate for the fixing solution or blix solution of 1,200 ml or less, and more preferably 800 ml or less, and even more preferably 600 ml or less.
  • a replenishment rate for the color developer of 700 ml or less is preferred, and 500 ml or less is particularly preferred. Additionally, a replenishment rate for the bleaching solution of 600 ml or less is preferred, and 300 ml or less is further preferred.
  • the effects are pronounced with color photographic materials for picture taking which use silver bromoiodide emulsions;
  • the film-swelling rate T 1/2 for the binder for the photographic emulsion layers is 10 seconds or less, more preferably where the thickness of all of the photographic structural layers is 18 ⁇ m or less and the film-swelling rate T 1/2 is 8 seconds or less.
  • Photographic structural layers refer to all of the hydrophilic colloid layers contributing to image formation on the same side of the support as that having the silver halide emulsion layers. These layers include, for example, antihalation layers (black colloidal silver antihalation layers and the like), underlayers, interlayers (simple interlayers or filter layers, ultraviolet absorbing layers and the like), protective layers and the like as well as the silver halide emulsion layers.
  • the thickness of the photographic structural layers is the total thickness of the above hydrophilic colloid layers and may be measured with a micrometer.
  • the film swelling rate T 1/2 of the binder for the silver emulsion layers in the silver halide color photographic material used in the present invention is 25 seconds or less.
  • gelatin is normally used for the hydrophilic binder employed in the coating of the silver halides of the silver halide color photographic material, although macromolecular polymers can also be used.
  • the film swelling rate T 1/2 of the binder must be 25 seconds or less.
  • the swelling rate T 1/2 of the binder can be measured using known techniques in the art. For example, it can be measured using a swellometer of the type described in A. Green, Photographic Science and Engineering , vol. 19, No. 2, pp. 124-129.
  • T 1/2 is defined as the time taken to reach half the saturated film thickness which is taken to be 90% of the maximum swollen film thickness which is achieved upon processing in a color developing solution at 30°C for 3 minutes and 15 seconds.
  • the film swelling rate taken as T 1/2 , is the time required to reach half the film thickness when the swollen film thickness is at a maximum.
  • the film swelling rate T 1/2 can be adjusted by adding a film hardener to the gelatin acting as the binder.
  • film hardeners used either alone or in combination include film hardeners of the aldehyde type, azylidine type (for example those described in PB Report 19921, US-A- 2,950,197, US-A- 2,964,404, US-A- 2,983,611, and US-A- 3,271,175, JP-B-46-40898, and JP-A-50-91315), isoxazolium type (for example those described in US-A- 3,321,323), epoxy type (for example those described in US-A- 3,047,394, DE-B- 1,085,663, GB-B- 1,033,518, and JP-B-48-35495), vinylsulfone type (for example those described in PB Report 19920, DE-B- 1,100,942, DE-B- 2,337,412, DE-B- 2,545,722, DE-B- 2,635,518 and DE-B- 2,742,308, GB-B- 1,251,091, and US-A- 3,539,644
  • the color developing agents to be used in the color developing solution and color development replenishing solution are primary aromatic amine compounds including known compounds which are widely used in various color photographic processes.
  • preferred color developing agents are:
  • color developing agents may be used alone, but may also be used in combination depending on the intended results. Examples of preferred combinations include (1) and (2), (1) and (3) as well as (2) and (3) of the above color developing agents.
  • the bromide ion concentration in the color developer is preferably within the range of 0.005 to 0.02 mol/l. It is preferable to keep the bromine compound content of the replenishment solution at no more than 0.005 mol/l. Generally, the bromine compound content of the replenishment solution ought to be reduced as the replenishment rate is reduced. In the present invention in particular, it is preferable for the replenishment solution to contain no bromine compounds since this provides the ability for a great reduction in the replenishment amount.
  • bromine compounds include potassium bromide, sodium bromide, lithium bromide and hydrobromic acid.
  • the color developer and the color developer replenisher may include preservatives, notably hydroxylamine, diethylhydroxylamine and triethylanolamine, and the compounds described in DE-A- (OLS) 2,622,950, the hydrazines described in JP-A-63-146041, sulfites and hydrogen sulfites.
  • various chelating agents may be incorporated in the system for the purposes of water softening and metal sequestering.
  • R is particularly preferably a methyl group or an ethyl group
  • M is preferably a hydrogen atom or a sodium atom.
  • the color developer to be used in the present invention can contain, either alone or in combination, pH buffers such as alkali metal carbonates, borates, or phosphates; antifoggants or development inhibitors such as iodine compounds, benzimidazoles, benzothiazoles and mercapto compounds; organic solvents such as diethylene glycol; development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium, amines and thiocyanates; nucleating agents such as sodium borohydride; auxiliary developers such as 1-phenyl-3-pyrazolidone; viscosity enhancers; and various chelating agents, such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid hydroxyethyliminodiacetic acid and the organic phosphonates described in Research Disclosure , No. 18170 (May 1979) in addition to the organic phosphonates described
  • the pH of the color developer and its replenisher is normally 9 or more, preferably 9.5 to 12, particularly preferably 9.5 to 11.0. In the above ranges, it is preferable to set the replenisher pH at a value which is higher than the color developer by about 0.05 to 0.5.
  • the temperature of the color development processing is 30 to 45°C and is preferably at a high temperature in order to achieve a greater degree of low-replenishment processing, and the development processing is preferably carried out at 35°C to 45°C, and particularly preferably at 38 to 42°C in the present invention.
  • the present invention can be employed with both an automatic processor and in manual processing, but it is preferably employed with an automatic processor.
  • processing with an automatic processor one or a plurality of color developer tanks can be used, and lower replenishment can be achieved by the use of a multi-stage sequential current replenishment system in which a plurality of tanks are employed and sequential flow into the subsequent tanks is achieved by replenishing a first tank.
  • a shielding means such as a floating lid, a seal using a high boiling liquid with a lower density than the developer, or a tank structure with a constricted opening as described in JP-A-63-216050.
  • the replenished water is preferably deionized water which has undergone an ion-exchange treatment or deionized water which has undergone a treatment such as reverse osmosis or distillation.
  • the color developer and color developer replenisher are prepared by progressively adding and dissolving the above chemicals in a fixed amount of water, and it is preferable to use deionized water described above as the water for the preparation.
  • bleaching agents are generally complex salts of chelating agents such as an aminocarboxylic acid, a polycarboxylic acid, an aminopolycarboxylic acid and ferric ion.
  • chelating agents such as an aminocarboxylic acid, a polycarboxylic acid, an aminopolycarboxylic acid and ferric ion.
  • preferred chelating agents which are used as complex salts with ferric ions include:
  • the ferric ion complexes may be used in the form of complex salts or they may be used by forming ferric ion complexes in solution using chelating agents such as an aminopolycarboxylic acid, an aminopolyphosphoric acid and a phosphonocarboxylic acid with ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate and ferric phosphate.
  • chelating agents such as an aminopolycarboxylic acid, an aminopolyphosphoric acid and a phosphonocarboxylic acid with ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate and ferric phosphate.
  • One type of complex salt may be used or two or more types of complex salt may be used when used in the form of a complex salt. In such cases, the combined use of chelating agents (1) and (4) is particularly preferred.
  • ferric salt when forming a complex salt in solution using a chelating agent and a ferric salt, one or more types of ferric salt may be used. Moreover, one or more types of chelating agent may be used. In addition, in all these cases, the chelating agent may be used in excess of the amount needed to form the ferric ion complex.
  • An aminopolycarboxylic acid iron complex is preferred of the iron complexes, and the addition amount for this complex is 0.1 to 1 mol/l and preferably 0.2 to 0.4 mol/l in the bleaching solution for a color photographic material for picture taking such as a color negative film, and is 0.05 to 0.5 mol/l and preferably 0.1 to 0.3 mol/l in the blix solution for this type of material. Further, with bleaching solutions or blix solutions for a color photographic material for prints such as a color paper, the addition amount is 0.03 to 0.3 mol/l and preferably 0.05 to 0.2 mol/l.
  • bleach accelerators can be incorporated in the bleaching solution and blix solution as desired.
  • Specific preferred examples of useful bleach accelerators are compounds having a mercapto group or a disulfide group because they have a large accelerating effect, and the compounds described in US-A- 3,893,858, DE-B- 1,290,812 and JP-A-5395630 are preferred.
  • the bleaching solution or blix solution used in the present invention can contain rehalogenating agents such as bromine compounds (for example, potassium bromide, sodium bromide and ammonium bromide), chlorine compounds (for example, potassium chloride, sodium chloride and ammonium chloride) or iodine compounds (for example, ammonium iodide).
  • bromine compounds for example, potassium bromide, sodium bromide and ammonium bromide
  • chlorine compounds for example, potassium chloride, sodium chloride and ammonium chloride
  • iodine compounds for example, ammonium iodide
  • corrosion inhibitors such as one or more types of inorganic acid or organic acids with a pH buffering capability such as boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate and tartaric acid and the alkali metal or ammonium salts thereof, ammonium nitrate and guanidine.
  • a pH buffering capability such as boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate and tartaric acid and the alkali metal or ammonium salts thereof, ammonium nitrate and guanidine.
  • the above mentioned bleaching solution is normally used in a pH range of 3 to 7, preferably 3.5 to 6.5, particularly 4.0 to 6.0. Furthermore, for the blix solution, the pH is 4 to 9, preferably 5 to 8, particularly 5.5 to 7.5. When the pH is above this range, bleaching imperfections tend to occur, and, when it is below this range, color imperfections are tend to occur in the cyan dye.
  • the fixing agents to be used in the fixing solution used after the processing with the blix solution or bleaching solution of the present invention are known fixing agents.
  • Examples include water-soluble silver halide solvents such as thiosulfates, e.g., sodium thiosulfate and ammonium thiosulfate; thiocyanates, e.g., sodium thiocyanates and ammonium thiocyanates; and thioureas and thioether compounds, e.g., ethylenebisthioglycolic acid and 3,6-dithia-1,8-octanediol, and these can be used either alone or in admixture.
  • the amount of fixing agent to be incorporated per liter is preferably 0.5 to 3 mol, and more particularly it is in the range of 1 to 2 mol for the processing of color photographic materials for picture taking, and is within the range of 0.5 to 1 mol for the processing of color photographic materials for prints.
  • the pH for the fixing solution used in the present invention is preferably 4 to 9 and particularly preferably 5 to 8.
  • the deterioration of the solution is marked when it is below this, and conversely staining tends to occur due to volatilization of ammonia from the ammonium salt present in the solution when the pH is higher than this.
  • the pH can be adjusted using hydrochloric acid, sulfuric acid, nitric acid, acetic acid, bicarbonate, ammonia, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate and the like as desired.
  • the blix solutions and fixing solutions to be used in the present invention contain, as preservatives, sulfites (such as sodium sulfite, potassium sulfite and ammonium sulfite), bisulfites (such as ammonium bisulfite, sodium bisulfite and potassium bisulfite), metabisulfites (such as potassium metabisulfite, sodium metabisulfite and ammonium metabisulfite) and other sulfite ion-releasing compounds, benzenesulfinic acid, para-toluenesulfinic acid and other aromatic sulfinic acids and salts thereof.
  • sulfites such as sodium sulfite, potassium sulfite and ammonium sulfite
  • bisulfites such as ammonium bisulfite, sodium bisulfite and potassium bisulfite
  • metabisulfites such as potassium metabisulfite, sodium metabisulfite and ammonium metabisulfite
  • Sulfites are normally used as preservatives. Ascorbic acid and carbonyl bisulfite adducts of carbonyl compounds and the like may also be used.
  • buffers may also be used as desired.
  • Washing, stabilization and other processing stages are generally undertaken after the fixing stage or blix stage, but it is also possible to use simplified processing methods, for example, where washing alone is undertaken or, conversely, where a stabilization processing stage alone is undertaken essentially without a washing stage.
  • the washing stage removes processing solution constituents which have adhered to or been absorbed into the color photographic material and the undesired constituents in the color photographic material and so has the effect of preserving the image stability and good film properties after processing.
  • the stabilization stage is a stage in which the image-storage properties are improved to a level which cannot be attained by washing.
  • the washing stage may involve a single tank, but more often it involves a multi-stage countercurrent washing system with two or more tanks.
  • the amount of water to be used in the washing stage can be varied depending on the type of color photographic material and the intended results, and it can be calculated, for example, using the method described in S.R. Goldwasser, "Water Flow Rates in Immersion-Washing of Motion Picture Film", The Journal of Motion Picture and Television Engineering , vol. 64, pp. 248-253, May 1955.
  • washing water in which calcium and magnesium levels have been reduced as described in JP-A-62-288838 as a countermeasure to this.
  • bactericides and antifungal agents e.g., compounds as described in The Journal of Antibacterial and Antifungal Agents, vol. 11, No. 5, pp. 207 to 223, and Hiroshi Horiguchi, Sakkin Bobai no Kagaku (Bactericidal and Antifungal Chemistry)
  • chelating agents such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid as water softeners.
  • a water amount of 100 ml to 1,500 ml per m 2 of color photographic material is normally used when economizing on the amount of washing water, and a range of 200 ml to 800 ml is particularly preferred in that this brings out the twin advantages of color image stability and water-saving effect.
  • the pH in the washing stage is normally within the range of 5 to 9.
  • various compounds are added to the stabilizing bath in order to stabilize the image.
  • various buffering agents to adjust the film pH after processing (for example, the combined use of borates, metaborates, borax, phosphates, carbonates, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acids, dicarboxylic acids, and polycarboxylic acids), and, in the same way as they can be added to the washing water, chelating agents, bactericides, formaldehyde and formaldehyde-releasing compounds such as hexamethylenetetramine as well as fluorescent brightening agents depending on the application.
  • ammonium salts such as ammonium chloride, ammonium sulfite, ammonium sulfate and ammonium thiosulfate.
  • the pH of the stabilizing bath is normally 3 to 8, but a low pH range of 3 to 5 is particularly preferred due to variations in the type of light-sensitive material and its intended use.
  • the present invention can be applied to the processing of various color photographic materials.
  • Typical examples of such color photographic materials include color negative films for general use and cinema, color reversal films for slides and television and the like.
  • Couplers which provide the three subtractive primary colors (namely, yellow, magenta and cyan) during color development are the most important of the color couplers, and the following couplers and the couplers described in the patents described in the previously cited RD 17643, VII-C and D can be used and are preferred in the present invention as specific examples of nondiffusion 4-equivalent and 2-equivalent couplers.
  • Known yellow couplers of the oxygen atom leaving type or known yellow couplers of the nitrogen atom leaving type are typical examples of yellow couplers which can be used.
  • ⁇ -Pivaloylacetoanilide-based couplers have outstanding fastness, particularly lightfastness of the color-forming dye, while ⁇ -benzoylacetoanilide-based couplers provide a high color density.
  • Hydrophobic 5-pyrazolone-based and pyrazoloazole-based couplers with ballast groups are suitable as magenta couplers which can be used in the present invention.
  • 5-Pyrazolone-based couplers in which the 3-position has been substituted with an arylamino group or an acylamino group are preferred from the standpoint of the hue and color density of the color forming dye.
  • Cyan couplers which can be used in the present invention include hydrophobic, nondiffusible naphtholic and phenolic couplers. Typical examples include 2-equivalent naphtholic couplers of the oxygen atom leaving type and these are preferred. Further, couplers able to form a cyan dye which is resistant to both moisture and heat are used preferably.
  • Typical examples of these are described in US-A- 3,772,002 and include phenolic cyan couplers with an ethyl or higher alkyl group in the meta position of the phenol nucleus, 2,5-diacylamino-substituted phenolic couplers, phenolic couplers with a phenylureido group in the 2-position and an acylamino group in the 5-position or, as described in EP-A- 161,626, 5-aminonaphtholic cyan couplers and the like.
  • Graininess can be improved by the combined use of a coupler in which the color forming dye has a suitable degree of diffusibility.
  • a coupler in which the color forming dye has a suitable degree of diffusibility.
  • actual examples of magenta couplers are described in, for example, US-A- 4,366,237, and specific examples of yellow, magenta and cyan couplers are described in, for example, EP-B- 96,570.
  • Dye-forming couplers and the special couplers mentioned above may form dimers and higher polymers.
  • Typical examples of polymerized dye-forming couplers are described in US-A- 3,451,820.
  • Specific examples of polymerized magenta couplers are described in US-A- 4,367,282.
  • Couplers which release a photographically useful group upon coupling can also be used for preference in the present invention.
  • the couplers in the patents described in the previously cited RD 17643, Section VII-F are useful as DIR couplers which release development inhibitors.
  • Couplers which release nucleating agents in the form of image or development accelerators or precursors thereof during development can be used in the photographic materials used in the present invention. Specific examples of these compounds are described in GB-B- 2,097,140 and GB-B- 2,131,188. In addition, it is also possible to use couplers which release DIR redox compounds as described in JP-A-60-185950 and couplers which release color-restoring dyes after split-off as described in EP-A- 173,302.
  • the couplers to be used in the present invention can be incorporated into the photographic material using various known dispersion methods.
  • Examples of high boiling organic solvents to be used in the oil-in-water dispersion method are described in US-A- 2,322,027.
  • specific examples of the processes, effects and impregnatable latexes used in the latex dispersion method are described in US-A- 4,199,363, DE-A- (OLS) Nos. 2,541,274 and DE-A- 2,541,230.
  • the double jet method was used for 1 minute, with stirring, to add an aqueous solution of silver nitrate (5 g as silver nitrate) and an aqueous solution of potassium bromide containing 0.15 g of potassium iodide to a vessel in which 30 g of gelatin and 6 g of potassium bromide had been added to 1 l of water and which was maintained at 60°C.
  • the double jet method was used to add an aqueous solution of silver nitrate (145 g as silver nitrate) and an aqueous solution of potassium bromide containing 4.2 g of potassium iodide.
  • the addition flow rate was accelerated so that the flow rate at the end of the addition was 5 times that at the start of the addition.
  • the soluble salts were removed by precipitation at 35°C and then the temperature was increased to 40°C, 75 g of gelatin were added and the pH was adjusted to 6.7.
  • the resulting emulsion comprised tabular grains with a projected surface area diameter of 0.98 ⁇ m and an average thickness of 0.138 ⁇ m and had a silver iodide content of 3 mol%.
  • the emulsion was chemically sensitized by the combined use of gold and sulfur sensitization.
  • aqueous gelatin solution containing polyarylamide with an average molecular weight of 8,000, sodium polystyrenesulfonate, polymethylmethacrylate grains with an average grain size of 3.0 ⁇ m, polyethylene oxide, and a film hardener as well as gelatin acting as the surface protective layer was used.
  • Anhydro-5,5'-dichloro-9-ethyl-3,3'-di(3-sulfopropyl)oxacarbocyanine hydroxide sodium salt was added as a sensitizing dye to the above emulsion in a proportion of 500 ml/mol of Ag and potassium iodide was added in a proportion of 200 mg/mol of Ag.
  • a photographic material was produced by preparing a coating solution by adding 4-hydroxy-6-methyl-1,3,3a,7-tetraazainddene and 2,6-bis(hydroxyamino)-4-diethylamino-1,3,5-triazine and nitron as stabilizers, trimethylol propane as a dry antifoggant and adding coating aids and film hardeners, coating the material onto both sides of a polyethylene terephthalate support simultaneously with the respective surface protective layers and drying.
  • the coated silver amount in this photographic material was 2 g/m 2 on each side.
  • the photographic material exhibited a percentage swelling of 120% as determined in accordance with the above described definition.
  • a heater was used to maintain a predetermined temperature both in the developing tank and the fixing tank, but cooling water was not used.
  • the processing tanks were filled with the following processing solutions: Developing Tank 400 ml of the above mentioned concentrated developer, 600 ml of water, and 10 ml of an aqueous solution containing 1.8 g of acetic acid; pH adjusted to 10.50 Fixing Tank 250 ml of the above mentioned concentrated fixing solution and 750 ml of water Washing Tank and cleaning tank Same composition as that in the above mentioned stock tank solution
  • the amount of developer to be circulated and stirred was set at 20 l/min.
  • the light-sensitive material was not developed, it was set at 6 l/min.
  • rollers at the crossover between development and fixation and between fixation and washing were each cleaned with 80 ml of water intermittently and automatically sprayed through 10 nozzles from the washing water stock tank.
  • the dry-to-dry processing time was set at 60 seconds as described above.
  • Table 1 shows the residual color after processing (the value obtained by measuring the transmitted optical density of the non-image portion using a green light).
  • Compound added to Fixing Solution Residual Color after Processing fresh properties
  • Transmitted Optical Density after 50°C-5 days Control 0.209 0.220
  • Compound A comparative 0.147 0.191
  • Compound I-(2) present invention
  • Compound I-(4) ( “ ) 0.149 0.149
  • Compound I-(12) ( “ ) 0.150 0.151
  • Compound II-(1) ( “ ) 0.151 0.153
  • Compound II-(5) ( “ ) 0.149 0.150
  • Compound II-(7) “ ) 0.148 0.149
  • Table 1 shows that all the fixing solutions comprising the present compounds exhibit a small residual color after processing.
  • a photographic material was prepared in the same manner as in Example 1, subjected to an X-ray exposure, and then subjected to development with a developer comprising 5 mmol/l of a compound used in the present invention, followed by fixation, and washing in the same manner as in Example 1.
  • Table 2 shows that photographic materials which have been processed with developers comprising the present compounds exhibit less residual color after processing.
  • a photographic material comprising 200 ml/mol Ag of a 10 -3 mol methanol solution of Compound I-(2) in the surface protective layer was processed with a developer free of this compound. As a result, the photographic material exhibited a residual color of 0.163 after processing.
  • Photographic materials Samples 301 to 307 were prepared in the same manner as in Example 1 except that various sensitizing dyes set forth below were incorporated into the materials, and then the materials were subjected to development in an automatic processor in the same manner as in Example 1. Sample No.
  • Sensitizing Dye (amount added mg/mol Ag) Compound Added to the Photosensitive Material (5 mmol/l) (Residual Color Density when a Compound of the Invention was not Used) - (Residual Color Density when a Compound of the Invention was Used) 301 A(500) I-(2) 0.072 302 B(500) II-(7) 0.074 303 C(400) II-(7) 0.073 304 D(500) I-(2) 0.073 306 E(500) II-(7) 0.070 306 F(500) II-(7) 0.074 307 G(500) II-(5) 0.073
  • a film was obtained by coating the coating solution thus prepared onto a polyethylene terephthalate film support together with a protective layer such that the coated silver amount was 3.5 g/m 2 and the coated gelatin amount (in both the emulsion layers and protective layer) was 3.0 g/m 2 .
  • the dry-to-dry time in the automatic processor used was set at 65 seconds.
  • Developer Sodium Ethylenediaminetetraacetate 1.0 g Sodium Hydroxide 9.0 g 5-Sulfosalicylic Acid 44.0 g Potassium Sulfite 100.0 g 5-Methylbenzotriazole 0.5 g Potassium Bromide 6.0 g N-Methyl-p-aminophenol Hemisulfate 0.4 g Hydroquinone 54.0 g Sodium p-Toluenesulfonate 30.0 g Water to make 1 l pH 11.7
  • Example 2 An identical aqueous solution to that used in Example 1 was used for the washing water and 250 ml of this solution was replenished per full size sheet (20 inch ⁇ 24 inch).
  • the residual color after processing was measured in the same manner as in Example 1.
  • the residual color density was found to be less than in the photographic material in which a compound of the present invention had not been used by 0.061.
  • a cubic monodisperse emulsion with an average grain size of 0.25 ⁇ m and an average silver iodide content of 1 mol% was prepared by simultaneously adding, over 60 minutes while maintaining the pAg at 7.8, an aqueous solution of silver nitrate and an aqueous solution of potassium iodide and potassium bromide to an aqueous gelatin solution kept at 50°C, in the presence of 4 ⁇ 10 -7 mol per mol Ag of potassium hexachloroiridate (III).
  • the pH on the film surface was adjusted to 5.5 with ascorbic acid, and coating was carried out in a silver amount of 3.4 g/m 2 on a polyethyleneterephthalate film (the measurement of the film surface pH was in accordance with the method described in JP-A-62-25745).
  • a gelatin layer was coated onto the emulsion layer to a coated gelatin amount of 1.0 g/m 2 .
  • the resulting samples were exposed to light, developed, and then the photographic properties were measured.
  • the developer formulation was as follows: Developer Hydroquinone 35.0 g N-Methyl-p-aminophenol Hemisulfate 0.8 g Sodium Hydroxide 13.0 g Potassium Triphosphate 74.0 g Potassium Sulfite 90.0 g Tetrasodium Ethylenediaminetetraacetate Dihydrate 1.0 g Potassium Bromide 4.0 g 5-Methylbenzotriazole 0.6 g 3-Diethylamino-1,2-propanediol 15.0 g Compound I-(2) 2.0 g Water to make 1 l pH 11.65
  • the fixing solution formulation was as follows: Ammonium Thiosulfate 150.0 g Sodium Sulfite 30.0 g Acetic Acid 30.0 g Water to make 1 l pH adjusted with NaOH to 5.00 Development 40°C 15 sec. Fixing 37°C 16 sec. Washing 12 sec. Dry to dry 67 sec.
  • the photographic properties (density Dmax, sensitivity) in the above samples had less residual color after processing (red density: 0.040).
  • a photographic material was prepared in the same manner as in Example 5, exposed, and then subjected to development in the same manner as in Example 5 except that 2.0 g/l of Compound II-(2) was added to the fixing solution instead of the developer.
  • the samples exhibited a small residual color with a red density of 0.042.
  • a silver halide emulsion was prepared comprising silver bromochloride (5 mol% silver bromide; average grain diameter: 0.25 ⁇ m) containing 1 ⁇ 10 -5 mol of Rh per mol of silver.
  • a gelatin solution was coated onto this emulsion layer as a protective layer in a gelatin amount of 1.0 g/m 2 .
  • Sodium p-dodecylbenzensulfonate was used as a coating aid for this protective layer, and the same compound as in the emulsion layer was used as a viscosity enhancer.
  • a model P-607 printer available from Dai Nippon Screen Co., Ltd. was used to expose the resulting samples via an optical wedge and development processing was carried out using the following developing solution and fixing solution formulations.
  • a sulfur-sensitized silver halide emulsion comprising 93 mol% of silver bromide and 7 mol% of silver iodide was prepared.
  • the average diameter of the silver halide grains present in the emulsion was 0.7 ⁇ m. 1 kg of this emulsion contained 0.52 mol of silver halide.
  • the film samples were subjected to an optical wedge exposure using a sensitometer and a light source with a color temperature of 2,854°K with a dark red filter (SC-74) made by Fuji Photo Film Co., Ltd. attached to the light source. After the exposure, development was carried out for 3 minutes at a temperature of 20°C using a developer with the following composition, stopping was effected, and fixing was then carried out using the following fixing solution after which the samples were washed.
  • SC-74 dark red filter
  • the residual color (transmitted optical density in the non-image areas) after processing is set forth in Table 5.
  • the double jet method was used to prepare a cubic monodisperse silver bromochloride emulsion with an average grain diameter of 0.3 ⁇ m (fluctuation coefficient: 0.13; silver iodide content: 0.1 mol%; silver bromide content: 33 mol%).
  • potassium bromide 100 mg of sodium p-dodecylbenzenesulfonate, 30 mg of 5-nitroindazole, 20 mg of 5-methylbenzotriazole, 1.5 g of a styrene/maleic acid copolymer and 15 g of a styrene/ butyl acrylate copolymer latex (average grain diameter: 0.25 ⁇ m), each per mol of silver halide, were added.
  • the sample was prepared by the simultaneous multi-layer coating of a protective layer containing 25 mg/m 2 of formaldehyde as a film hardener and 30 mg/m 2 of sodium 1-decyl-2-(3-isopentyl)succinate-2-sulfonate as an extender so that the gelatin amount was 1.2 g/m 2 .
  • These samples were processed for 30 seconds at a temperature of 28°C using a GR-27 automatic processor made by Konica Corporation and under developing conditions using the Konica Developer CMD-651K and the Konica Fixer CGL-851 containing 2.0 g/l of each compound as set forth in Table 6.
  • Sensitizing Dye Compound added (Residual Color Density when a Compound of the Invention Was Not Used) - (Residual Color Density when a Compound of the Invention Was Used) 901 A I-(2) 0.051 902 B I-(2) 0.053 903 C I-(4) 0.053 904 A I-(4) 0.049 905 B II-(7) 0.048 906 C II-(7) 0.050
  • a photographic material was prepared in the same manner as in Example 9, exposed, and then subjected to development in the same manner as in Example 9 except that the compound used in the present invention was added to the developer in stead of the fixing solution.
  • the results obtained are set forth in Table 7 below.
  • Sample No. Sensitizing Dye Compound added (Residual Color Density when a Compound of the Invention Was Not Used) - (Residual Color Density when a Compound of the Invention Was Used) 1001 A I-(2) 0.055 1002 B I-(2) 0.057 1003 C I-(4) 0.056 1004 A I-(4) 0.053 1005 B II-(7) 0.053 1006 C II-(7) 0.056
  • Sample 1101 was prepared by multi-layer coating of the various layers thereof with the compositions shown below onto a subbed cellulose triacetate film support.
  • each of the constituents denote the amounts coated given in units of g/m 2 , while for the silver halides they denote the coated amount calculated as silver.
  • the figures corresponding to the sensitizing dyes and the compounds used in the present invention denote the molar unit for the coated amount with respect to 1 mol of silver halide in the same layer.
  • First Layer (Antihalation Layer) Black colloidal silver 0.18 Gelatin 0.48
  • Second Layer (Interlayer) 2,5-Di-t-pentadecylhydroquinone 0.18 EX-1 0.07 EX-3 0.02 EX-12 0.002 U-1 0.06 U-2 0.08 U-3 0.10 HBS-1 0.10 HBS-2 0.02 Gelatin 1.24
  • Third Layer (First Red-sensitive Emulsion Layer) Monodisperse silver bromoiodide emulsion (silver iodide content: 6 mol%; average grain diameter: 0.6 ⁇ m; grain diameter fluctuation coefficient: 0.15) 0.55 Sensitizing dye I 6.9 ⁇ 10 -5 Sensitizing dye II 1.8 ⁇ 10 -5 Sensitizing dye III 3.1 ⁇ 10 -4 Sensitizing dye IV 4.0 ⁇ 10 -5 EX-2 0.350 HBS-1 0.005 EX-10 0.020 Gelatin 1.45
  • Fourth Layer (Second Red-sensitive Emulsion Layer) Tabular silver bromoiodide emulsion (
  • Gelatin Hardener H-1 and a surface active agent were incorporated into each layer.
  • Sample 1101 had a total photographic structural layer thickness of 22 ⁇ m and a film swelling rate T 1/2 of 12 seconds.
  • Samples 1101, 1102 and 1103 thus prepared were cut into 35 mm widths and then subjected to a standard exposure in a camera, 1 m 2 of each was subjected to mixed processing per day by means of the following processing using an automatic processor and this was continued for 10 days.
  • the transmitted magenta densities in the unexposed areas of the processed samples were measured at the beginning (fresh processing) and the end (running processing) of the above processing using Model X Light 310 photographic densitometer.
  • the running processed samples were stored for 1 week under conditions of a relative humidity of 70% at a temperature of 60°C to evaluate the changes in the transmitted magenta density over this period.
  • Sample 1201 was prepared by multi-layer coating of various layers with the compositions shown below onto a subbed cellulose triacetate film support.
  • each of the components denote coated amounts in g/m 2 , while for the silver halides they denote the coated amount calculated as silver.
  • the figures corresponding to the sensitizing dyes and the compounds used in the present invention denote molar units for the coated amount with respect to 1 mol of silver halide in the same layer.
  • First Layer (Antihalation layer) Black Colloidal Silver 0.2 Gelatin 1.2 Ultraviolet Absorbent UV-1 0.05 Ultraviolet Absorbent UV-2 0.1 Ultraviolet Absorbent UV-3 0.1 Dispersing Oil OIL-1 0.02
  • Second Layer (Interlayer) Fine silver bromide grains (average grain size: 0.07 ⁇ m) 0.15 Gelatin 1.2
  • Third Layer (First Red-sensitive Emulsion Layer) Monodisperse silver bromoiodide emulsion (silver iodide content: 6 mol%; average grain diameter: 0.4 ⁇ m; grain diameter fluctuation coefficient: 0.15) 1.42 Gelatin 1.1 Sensitizing Dye A 2.0 ⁇ 10 -4 Sensitizing Dye B 1.0 ⁇ 10 -4 Sensitizing Dye C 0.3 ⁇ 10 -4 Cp-b 0.35 Cp-c 0.052 Cp-d 0.047 D-1 0.023 D-2 0.035 HBS-1 0.10 HBS-2 0.10
  • Fourth Layer (Interlayer) Gelatin 1.0 Cp-b
  • Stage Processing Time Processing Temperature Replenishment Rate Tank Capacity Color Development 1 min 30 sec 37.8°C 350 ml/m 2 10 l Bleaching 30 sec 37.8°C 130 ml/m 2 5 l Fixing 1 min 15 sec 37.8°C 500 ml/m 2 10 l Stabilization (1) 15 sec 35°C (3-stage countercurrent system in which water flows backward) 5 l Stabilization (2) 15 sec 35°C 5 l Stabilization (3) 15 sec 35°C 350 ml/m 2 5 l Drying 1 min 55°C
  • the replenishment rates are per m 2 .
  • the present invention inhibits an increase in the magenta density of the unexposed areas and is effective in inhibiting an increase in the cyan density in the unexposed areas during storage at an elevated temperature and a high humidity.
  • a multi-layer color printing paper with the following layer structures was prepared on a paper support which had been laminated on both sides with polyethylene.
  • the coating solutions were prepared as described below.
  • the following blue-sensitizing dyes were added to a silver bromochloride emulsion (cubic; a 3:7 mixture (silver molar ratio) of grains with an average grain size of 0.88 ⁇ m and grains with an average grain size of 0.70 ⁇ m; fluctuation coefficients in the grain size distributions were 0.08 and 0.10, each emulsion containing 0.2 mol% of silver bromide localized at the grain surface) respectively in amounts of 2.0 ⁇ 10 -4 moles per mol of silver halide in the large-sized emulsion and respectively in amounts of 2.5 ⁇ 10 -4 moles per mol of silver halide in the small-sized emulsion, and after this sulfur sensitization was carried out.
  • the above emulsified dispersion and this emulsion were mixed and dissolved to prepare a first coating solution with the composition given below.
  • the coating solutions for the second layer to the seventh layer were also prepared by methods similar to that for the first layer coating solution.
  • Sodium 1-oxy-3,5-dichloro-s-triazine was used as a gelatin hardener in each layer.
  • the following compound was added to the red-sensitive emulsion layer in an amount of 2.6 ⁇ 10 -3 mol per mol of silver halide.
  • 1-(5-methylureidophenyl)-5-mercaptotetrazole was added to the blue-sensitive emulsion layer, green-sensitive emulsion layer and red-sensitive emulsion layer in amounts of 8.5 ⁇ 10 -5 mol, 7.7 ⁇ 10 -4 mol and 2.5 ⁇ 10 -4 mol per mol of silver halide, respectively.
  • each layer is given below.
  • the figures represent coated amounts (g/m 2 ). With the silver halide emulsions, they represent the coated amounts calculated in terms of silver.
  • First Layer (Blue-sensitive Layer) Silver bromochloride emulsion as mentioned above 0.30 Gelatin 1.86 Yellow Coupler (ExY) 0.82 Color Image Stabilizer (Cpd-1) 0.19 Solvent (Solv-3) 0.35 Dye Stabilizer (Cpd-7) 0.06
  • Second Layer (Color Stain-inhibiting Layer) Gelatin 0.99 Color stain inhibitor (Cpd-5) 0.08 Solvent (Solv-1) 0.16 Solvent (Solv-4) 0.08
  • each of the samples was subjected to continuous processing (running test) comprising the following processing stages and a paper processing machine until the color development tank capacity had been replenished twice.
  • Processing Stage Temperature Time Replenisher Tank Capacity Color Development 38°C 20 sec. 161 ml 17 l Blix 35-38°C 20 sec. 215 ml 17 l Rinse (1) 35-38°C 7 sec. - 10 l Rinse (2) 35-38°C 7 sec. - 10 l Rinse (3) 35-38°C 6 sec. 350 ml 10 l Drying 70-80°C 30 sec.
  • compositions of the processing solutions used were as given below.
  • Color Developer Running Solution Replenisher (g) Water 800 ml 800 ml Ethylenediamine-N,N,N,N-tetramethylene Phosphonate 1.5 2.0 Potassium Bromide 0.015 - Triethanolamine 8.0 12.0 Sodium Chloride 1.4 - Potassium Carbonate 25 25 N-Ethyl-N-( ⁇ -methanesulfonamidoethyl)-3-methyl-4-aminoaniline Sulfate 5.0 7.0 N,N-Bis(carboxymethyl)hydrazine 5.5 7.0 Water to make 1,0000 ml 1,000 ml pH (25°C) 10.05 10.45 Blix Solution (The tank solution and the replenisher were the same.) Water 400 ml Compound I-(2) 2.0 g Thiosulfate (70% aq.
  • Ion-exchanged water (calcium and magnesium concentrations: 3 ppm or less each)
  • the reflected density based on the residual color from sensitizing dye in the unexposed area was markedly improved and lower than a photographic material which did not contain a compound as used in the present invention by 0.049.
  • a 1 N aqueous solution of silver nitrate and an aqueous solution containing 0.988 mol of potassium bromide and 0.012 mol of potassium iodide were mixed in the double jet process while the pAg of the system was appropriately controlled to obtain a silver bromoiodide emulsion.
  • the emulsion was then subjected to gold sensitization and sulfur sensitization to obtain an optimum sensitization.
  • an emulsion of tetradecahedral silver bromoiodide grains having an average grain diameter of 0.6 ⁇ m and containing (100) plane in a proportion of 86% was obtained.
  • aqueous gelatin solution and the above emulsion were simultaneously coated on a polyethylene-laminated paper with the emulsion kept in contact with the support in amounts such that the coated amount of the aqueous gelatin solution and the emulsion reached 1.5 g/m 2 and 2.25 g/m 2 , calculated in terms of gelatin, respectively, to prepare photographic materials.
  • the residual color is preferably 0.09 or less as represented by the figures in Table 10. If this value exceeds this range, the results can be recognized as residual color under a careful observation, and the products thus obtained cannot be put into commercial use. If this value exceeds 0.1, the results can be recognized as remarkable residual color.
  • a development processing kit comprising Part (A), Part (B) and Part (C) was prepared.
  • Part (A) (to be diluted to 10 l of developer) Potassium Hydroxide 291 g Potassium Sulfite 442 g Sodium Hydrogencarbonate 75 g Boric Acid 10 g Diethylene Glycol 120 g Ethylenediaminetetraacetic Acid 17 g 5-Methylbenzotriazole 0.6 g Hydroquinone 300 g 1-Phenyl-4,4-dimethyl-3-pyrazolidone 20 g Water to make 2.5 l pH 11.0
  • Part (B) (to be diluted to 10 l of developer)
  • Acetic Acid (glacial) 3 g 1-Phenyl-3-pyrazolidone 15 g Water to make 250 ml
  • Part (C) (to be diluted to 10 l of developer)
  • a starter having the following composition was prepared. Starter Acetic Acid (glacial) 270 g Potassium Bromide 300 g Water to make 1.5 l
  • the starter was then added to the solution in an amount of 20 ml per l of the solution.
  • a photographic material (unexposed) as prepared in Example 1 was then subjected to the following development in a roller conveyor type automatic processor system. Processing Stage Temperature Processing Time Development 35°C 12.5 sec. Fixing 30°C 10 sec. Rinse and Squeeze 20°C 12.5 sec. Drying 50°C 12.5 sec.
  • a photographic material was exposed to X-ray in the same manner as in Example 1, and then subjected to development with the same developer, fixing solution and rinse solution as used in Example 16.
  • Photographic materials 1801 to 1807 were prepared using the following sensitizing dyes in the same manner as in Example 16, and then subjected to development in an automatic processor in the same manner as in Example 16.
  • Sample No. Sensitizing Dye Amount Added Ag/mol Ag
  • Compound Added to Fixing Solution Compound Added to Fixing Solution
  • Residual Color Density When a Compound of the Invention Was Not Used - (Residual Color Density When a Compound of the Invention Was Used)
  • a photographic material was prepared in the same manner as in Example 4, exposed to light, and then subjected to development and fixing with a developer and a fixing solution as used in Example 4 in the same manner as in Example 4.
  • Example 16 The same aqueous solution as used in Example 16 was used as a rinse solution.
  • the replenishment rate was 250 ml per full-size (20 inch ⁇ 24 inch) sheet.
  • the same sample was similarly developed, and then fixed with a solution obtained by adding 1.6 g/l of Compound III(6) to GR-F1.
  • a double jet process was conducted at a temperature of 60°C with the pAg and pH values of the system controlled to 8 and 2.0, respectively, to obtain a monodisperse emulsion of cubic silver bromoiodide having an average grain diameter of 0.20 ⁇ m and containing a silver iodide content of 2.0 mol%.
  • a part of the emulsion was used as core on which the following growth was effected.
  • an ammonia solution of silver nitrate and a solution containing potassium iodide and potassium bromide were added to a solution containing these core grains and gelatin at a temperature of 40°C with the pAg and pH of the system controlled to 9.0, respectively, in a double jet process to form a first coat layer containing 30 mol% of silver iodide.
  • an ammonia solution of silver nitrate and a potassium bromide solution were added to the system with the pAg and pH of the system controlled to 9.0, respectively, in a double jet process to form a second coat layer of pure silver bromide.
  • a monodisperse emulsion of cubic silver bromoiodide grains having an average diameter of 0.57 ⁇ m was prepared (E-1). The emulsion had an average silver iodide content of 2.0 mol%.
  • Emulsion (E-1) To the Emulsion (E-1) were added the following sensitizing dyes A and B in the following amounts. The emulsion was then subjected to optimum gold-sulfur sensitization with 8 ⁇ 10 -7 mol of a chloroaurate, 7 ⁇ 10 -6 mol of sodium thiosulfate, and 7 ⁇ 10 -4 mol of ammonium thiocyanate. The emulsion thus sensitized was stabilized with 2 ⁇ 10 -2 mol of 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene. The gelatin concentration of the emulsion was adjusted so that the amount of gelatin per side was 2.25 g/m 2 .
  • the following additives were added to the emulsion and the protective film solution.
  • the following film hardener was then added so that the melting time was 20 minutes.
  • the above emulsion, the film hardener and the additives as described subsequently were added to the system so that the melting time was 20 minutes.
  • a protective layer having a gelatin content of 1.15 g/m 2 per side was prepared.
  • the above emulsion and the protective layer thus prepared were simultaneously coated in a multi-layer structure onto both sides of a subbed polyester film support at a coating rate of 50 m/min.
  • the silver halide emulsion layer (viscosity: 11 cP; surface tension: 35 dyn/cm; coat film thickness: 50 ⁇ m) and the protective layer (viscosity: 11 cP; surface tension; 25 dyn/cm; coat film thickness: 20 ⁇ m) were sequentially coated on the support to obtain a photographic material, Sample 2101.
  • the photographic material had a silver content of 45 mg/cm 2 .
  • a matting agent comprising polymethyl methacrylate grains having an average diameter of 5 ⁇ m and 7 mg of colloidal silica having an average grain diameter of 0.013 ⁇ m were added to the system.
  • the film hardener content of each layer was adjusted so that the melting time thereof was 20 minutes as determined by the following method.
  • the melting time is defined as the time between when a 1 cm ⁇ 2 cm piece of the sample is immersed in a 1.5% sodium hydroxide solution kept at a temperature of 50°C and when the emulsion layer begins to be eluted.
  • sensitivity and fog were measured in the following manner. Specifically, the sample was clamped by two sheets of optical wedges having a mirror-symmetrical arrangement of density gradient, and exposed to light from a light source with a color temperature of 5,400°K from both sides thereof at the same exposure level for 1/12.5 seconds.
  • Development was effected in accordance with the following steps using a roller conveyor type automatic processor which requires a total processing time of 45 seconds. Processing Temperature Processing Time Insertion - 1.2 sec. Development + transfer 35°C 14.6 sec. Fixing + transfer 33°C 8.2 sec. Rinse + transfer 25°C 7.2 sec. Squeeze 40°C 5.7 sec. Drying 45°C 8.1 sec. Total 45.0 sec.
  • the automatic processor used in this example had the following characteristics:
  • a rubber roller was used.
  • the rubber roller in the transfer portion was made of silicone rubber (hardness: 48), and that in the processing solution was made of EPDM (hardness: 46), an ethylene propylene rubbers.
  • the rubber roller had a maximum surface roughness Dmax of 4 ⁇ m.
  • the developer replenishment rate was 20 cc/quarter.
  • the fixing solution replenishment rate was 45 cc/quarter.
  • the amount of washing water used was 1.5 l/min.
  • the air flow in the drying portion was 11 m 2 /min.
  • the heater capacity was 3 KW (200 V).
  • the total processing time was 45 seconds as mentioned above.
  • Composition of Developer and Fixing Solution Developer-1 Potassium Sulfite 65.0 g Hydroquinone 25.0 g 1-Phenyl-3-pyrazolidone 2.5 g Boric Acid 10.0 g Sodium Hydroxide 21.0 g Triethylene Glycol 17.5 g 6-Methylbenzotriazole 0.06 g 5-Nitroindazole 0.14 g Glutaraldehyde Bisulfite 15.0 g Acetic Acid (glacial) 16.0 g Potassium Bromide 4.0 g Triethylenetetraminehexaacetic Acid 2.5 g Water to make 1 l Fixing Solution-1 Ammonium Thiosulfate 130.9 g Sodium Sulfite (anhydrous) 7.3 g Boric Acid 7.0 g Acetic Acid (90 wt% aq. soln.) 5.5 g Sodium Acetate Trihydrate 25.8 g Aluminum
  • the residual coloration was then evaluated.
  • the transmitted optical density was measured in the non-image area using green light
  • the samples according to the present invention have outstanding sensitivity, fogging, residual coloring characteristics and the like, and it can be seen that they are suitable for ultra-rapid processing.
  • Example 7 A photographic material was processed in the same manner as in Example 7 except that the compounds to be added to the fixing solution were altered as set forth in Table 16 below.
  • Compound Added to Fixing Solution Residual Color after Processing (Transmitted Optical Density) (Control) 0.211 (a) (Comparative Example) 0.209 (b) ( “ ) 0.200 (c) ( “ ) 0.158 III-(6) ( “ ) 0.141 III-(9) ( “ ) 0.143
  • Example 8 The same photographic material as used in Example 8 was exposed to light in the same manner as in Example 8. The photographic material thus exposed was then developed with a developer having the following composition at a temperature of 20°C for 3 minutes, stopped, fixed with the following fixing solution, and rinsed.
  • the residual coloration after processing (transmitted optical density in the non-image portion) is set forth in Table 17.
  • Developer Water 500 ml N-methyl-p-aminophenol 2.2 g Sodium Sulfite (anhydrous) 96.0 g Hydroquinone 8.8 g Sodium Carbonate (monohydrate) 56.0 g Potassium Bromide 5.0 g Compound III-(6) 1.7 g Water to make 1 l
  • the double jet method was used for 1 minute, with stirring, to add an aqueous solution of silver nitrate (5 g as silver nitrate) and an aqueous solution of potassium bromide containing 0.15 g of potassium iodide to a vessel in which 30 g of gelatin and 6 g of potassium bromide had been added to 1 l of water and which was maintained at 60°C.
  • the double jet method was used to add an aqueous solution of silver nitrate (145 g as silver nitrate) and an aqueous solution of potassium bromide containing 4.2 g of potassium iodide. The addition flow rate was accelerated so that the flow rate at the end of addition was 5 times that at the start of addition.
  • the soluble salts were removed by precipitation at 35°C and then the temperature was raised to 40°C, 75 g of gelatin were added and the pH was adjusted to 6.7.
  • the resulting emulsion comprised tabular grains with a projected surface area diameter of 0.98 ⁇ m and an average thickness of 0.138 ⁇ m and had a silver iodide content of 3 mol%.
  • the emulsion was chemically sensitized by the combined use of gold and sulfur sensitization.
  • a photographic material was produced by preparing a coating solution by adding 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene and 2,6-bis(hydroxyamino)-4-diethylamino-1,3,5-triazine, trimethylol propane as a dry antifoggant and adding coating aids and film hardeners, coating the material onto both sides of a polyethylene terephthalate support simultaneously with the respective surface protective layers and drying the material.
  • the coated silver amount in this photographic material was 3.7 g/m 2 on each side.
  • the developer and the fixing solution (1) used had the following compositions: Developer Diethylenetriaminepentaaceic Acid 2 g 1-Phenyl-3-pyrazolidone 2 g Hydroquinone 30 g 5-Nitroindazole 0.25 g 5-Methylbenzotriazole 0.02 g Potassium Bromide 1 g Sodium Sulfite (anhydrous) 60 g Potassium Hydroxide 30 g Potassium Carbonate 5 g Boric Acid 6 g Diethylene Glycol 20 g Glutaraldehyde 5 g Water to make 1 l pH 10.50 Fixing Solution (I) Ammonium Thiosulfate 175 g Sodium Sulfite (anhydrous) 20.0 g Boric Acid 8.0 g Disodium ethylenediaminetetraacetate dihydrate 0.1 g Aluminum Sulfate 15.0 g Sulfuric Acid 2.0 g Acetic Acid (glacial) 22.0 g Compound III-(6) 1.7 g Water to make 1.0 l
  • the above-mentioned photographic material samples were each processed in an amount of 500 quarter sheets under the following conditions.
  • the residual coloration caused by sensitizing dyes in the processing solution was as follows: Compound Added to Fixing Solution Upon Replenishment with 60 ml of Fixing Solution per Quarter Sheet Upon Replenishment with 30 ml of Fixing solution per Quarter Sheet Amount of I-ions in the Fixing Solution Residual Color Amount of I-ions in the Fixing Solution Residual Color Control 0.93 mmol/l Slightly pink residual color 1.87 mmol/l Much pink residual color, cannot be used for diagnosis III-(6) 0.92 mmol/l absolutely no problem 1.91 mmol/l absolutely no problem
  • Example 12 The same procedures as conducted in Example 12 was repeated except that the compounds as used in the present invention to be added to the fixing solution were altered as set forth in Table 21.
  • the present invention inhibits the increase in the magenta density of the unexposed areas and is effective in inhibiting the increase in the cyan density in the unexposed areas during storage at an elevated temperature and a high humidity.
  • Example 13 The same procedures as described in Example 13 were repeated except that the compounds as used in the present invention to be incorporated in the blix solution were replaced by III-(6) in an amount of 1.7 g/l.
  • the reflected density based on the residual color from the sensitizing dye in the unexposed area was markedly improved and was lower than a photographic material which did not contain a compound as used in the present invention by 0.055.

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Claims (7)

  1. Verfahren zur Verarbeitung eines photographischen Silberhalogenidmaterials, umfassend die Verarbeitung eines spektral sensibilisierten, photographischen Silberhalogenidmaterials mit einer Verarbeitungslösung, die eine Verbindung enthält, dargestellt durch die allgemeine Formel (I) oder (II) oder ein Salz davon
    Figure 02110001
    worin Z1 eine nichtmetallische Atomgruppe bedeutet, die benötigt wird, um einen ungesättigten Ring zu bilden; Y1 bedeutet ein Sauerstoffatom, ein Schwefelatom oder
    Figure 02110002
    wobei R11 ein Wasserstoffatom oder eine Alkylgruppe bedeutet; R1 bedeutet eine Alkylgruppe, die mit einer Amino-, Dialkylamino- oder Sulfonamidogruppe substituiert ist; und X1 bedeutet ein Sauerstoffatom
    Figure 02110003
    worin Z2 eine nichtmetallische Atomgruppe bedeutet, die benötigt wird, um einen ungesättigten Ring zu bilden; Y2 bedeutet ein Sauerstoffatom, ein Schwefelatom oder
    Figure 02120001
    wobei R12 dieselbe Bedeutung hat wie R11; R2 bedeutet eine Alkylgruppe, die mit einer Aminogruppe, einer Dialkylaminogruppe oder einer Sulfonamidogruppe substituiert ist; X2 bedeutet ein Sauerstoffatom, eine Methylengruppe oder
    Figure 02120002
    wobei R22 dieselbe Bedeutung hat wie R11; oder eine Verbindung, dargestellt durch die allgemeine Formel (III):
    Figure 02120003
    wobei Z eine nichtmetallische Atomgruppe bedeutet, die benötigt wird, um einen ungesättigten Ring zu bilden; und R bedeutet eine Alkylgruppe, substituiert mit einer Sulfogruppe, einer Dialkylaminogruppe oder einer Phosphonsäuregruppe, eine Arylgruppe, eine Acylgruppe, eine Allylgruppe oder eine Alkansulfonylgruppe; Verbindung (III) kann in Form eines tautomeren Enols vorliegen.
  2. Verfahren zur Verarbeitung eines photographischen Silberhalogenidmaterials nach Anspruch 1, wobei der durch Z1 oder Z2 gebildete ungesättigte Ring ein Benzolring, ein Naphtalinring oder ein 5- oder 6-gliedriger heterozyklischer Ring ist.
  3. Verfahren zur Verarbeitung eines photographischen Silberhalogenidmaterials nach Anspruch 2, wobei der durch Z1 oder Z2 gebildete heterozyklische Ring ein Pyridinring, ein Pyrimidinring, ein Pyrazinring, ein Furanring, ein Thienring, ein Pyrrolring, ein Triazinring, ein Imidazolring, ein Chinazolinring, ein Purinring, ein Chinolinring, ein Acridinring, ein Indolring, ein Thiazolring, ein Oxazolring, ein Selenazolring, ein Furazalanring oder ein heterozyklischer Ring ist umfassend einen Benzo- oder Naphthoring kondensiert damit.
  4. Verfahren zur Verarbeitung eines photographischen Silberhalogenidmaterials nach Anspruch 1, wobei R11 und R12 eine Alkylgruppe bedeuten, substituiert mit einer Dialkylaminogruppe oder eine unsubstituierte Alkylgruppe.
  5. Verfahren zur Verarbeitung eines photographischen Silberhalogenidmaterials nach Anspruch 1, wobei Y1 ein Schwefelatom bedeutet und X2 bedeutet -O- oder -NH-.
  6. Verfahren zur Verarbeitung eines photographischen Silberhalogenidmaterials nach Anspruch 1, wobei der durch Z gebildete ungesättigte Ring ein Benzolring, ein Naphtalinring oder eine 5- oder 6-gliedriger heterozyklischer Ring ist.
  7. Verfahren zur Verarbeitung eines photographischen Silberhalogenidmaterials nach Anspruch 6, wobei der durch Z gebildete heterozyklische Ring ein Pyridinring, ein Pyrimidinring, ein Pyrazinring, ein Furanring, ein Thienring, ein Pyrrolring, ein Triazinring, ein Imidazolring, ein Chinazolinring, ein Purinring, ein Chinolinring, ein Acridinring, ein Indolring, ein Thiazolring, ein Oxazolring, ein Selenazolring, ein Furazalanring oder ein heterozyklischer Ring ist, umfassend einen Benzo- oder Naphthoring kondensiert damit.
EP90121044A 1989-11-02 1990-11-02 Photographisches Silberhalogenidmaterial, Verarbeitungslösung und dessen Verarbeitungsverfahren Expired - Lifetime EP0426193B1 (de)

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JP286660/89 1989-11-02
JP1286660A JP2632055B2 (ja) 1989-11-02 1989-11-02 ハロゲン化銀感光材料用の処理液および処理方法
JP289312/89 1989-11-07
JP1289312A JP2579223B2 (ja) 1989-11-07 1989-11-07 ハロゲン化銀感光材料、ハロゲン化銀感光材料の処理液および処理方法

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IT1254509B (it) * 1992-03-06 1995-09-25 Minnesota Mining & Mfg Metodo per il trattamento di un materiale radiografico agli alogenuri d'argento
DE69636024T2 (de) * 1995-08-23 2006-08-31 Fuji Photo Film Co., Ltd., Minami-Ashigara Verfahren zur Verarbeitung lichtempfindlichen Silberhalogenidfarbmaterials

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EP0413314A1 (de) * 1989-08-15 1991-02-20 Fuji Photo Film Co., Ltd. Silberhalogenid enthaltendes photographisches Material

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US2891862A (en) * 1956-11-06 1959-06-23 Eastman Kodak Co Stabilized photographic silver halide emulsions
BE596987A (de) * 1959-11-12
BE789918A (fr) * 1971-10-12 1973-04-11 Lilly Co Eli Benzothiazoles dans la lutte contre les organismes phytopathogenes
JPH0612416B2 (ja) * 1985-09-13 1994-02-16 富士写真フイルム株式会社 ハロゲン化銀写真感光材料の処理方法
US4906553A (en) * 1988-05-09 1990-03-06 Fuji Photo Film Co., Ltd. Processing process for silver halide black and white photographic materials

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