Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
  • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
  • G03C5/29—Development processes or agents therefor
  • G03C5/31—Regeneration; Replenishers
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • 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
  • G03C1/061—Hydrazine compounds
• • 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
  • G03C5/29—Development processes 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
  • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
  • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
  • G03C5/29—Development processes or agents therefor
  • G03C5/305—Additives other than developers

Definitions

• the present invention relates to a method for processing a silver halide photographic material. More particularly, the present invention relates to a method for processing a silver halide photographic material which minimizes silver stain (also referred to as "silver sludge") attached to a development tank, development rack or roller, to facilitate the maintenance of an automatic developing machine.
• silver stain also referred to as "silver sludge”
• the development of a silver halide photographic material is often done with an automatic developing machine for the sake of rapidity, simplicity and handleability.
• the developer comprises a large amount of sulfites to minimize the so-called air oxidation of the developing agent for the purpose of maintaining its development activity.
• automatic developing machines there have heretofore been used a suspension type automatic developing machine, an automatic developing machine for motion picture film, a roller carrying automatic developing machine, a rotary automatic developing machine for disc film, rotary drum automatic developing machine, a reel winding automatic developing machine, etc.
• These automatic developing machines are operated in various ways.
• roller carrying type automatic developing machines are mainly used because of ease of operation, rapidity, stability, etc.
• An automatic developing machine for use in the processing of a black-and-white light-sensitive material normally comprises a development tank, fixing tank, and washing tank. These tanks are each provided with a light-sensitive material passage through which the light-sensitive material is sequentially and automatically supplied. Therefore, the surface area of each processing solution in contact with air is large, causing problems of great deterioration of the processing solution by air oxidation and great evaporation of the processing solution.
• the roller carrying type automatic developing machines are apt to have a great opening ratio.
• the term "opening ratio" as used herein means a "ratio obtained by dividing the area cm2 of the processing solution in the development tank in contact with air by the volume cm3 of the development tank.
• the product of twice the diameter of the roller and the length of the roller is added to the area (the whole area of the surface of the solution).
• the opening ratio of commonly used automatic developing machines is normally higher than 0.05 and up to about 1.5.
• the replenishment rate of the processing solution is determined by the compensation for the processing of the photographic light-sensitive material, the compensation for air oxidation due to ageing, and the compensation for the evaporation loss. Therefore, by reducing the opening ratio, the deterioration of the processing solution due to air oxidation can be prevented and the concentration due to evaporation can be suppressed, enabling a drastic reduction of the replenishment rate.
• the processing with a developer containing a compound having a dissolving effect on silver halide such as a sulfite, a thioether, an imidazole, and a thiosulfate often causes silver stain (also referred to as "silver sludge") in the developer.
• silver stain also referred to as "silver sludge”
• silver stain attaches to and accumulates on the development tank or roller and then adheres to the photographic light-sensitive material being processed, causing stain in the image. Therefore, the apparatus requires regular cleaning and maintenance.
• the photographic light-sensitive material to be used in the contact work is required to exhibit photographic properties that give high enough image contrast and black density to clearly distinguish between the image portion and the nonimage portion to improve the image reproducibility.
• a fine particle emulsion is preferably used.
• a method which comprises the use of a silver chloride emulsion or a silver bromochloride emulsion with a low silver bromide content comprising a desensitizer such as rhodium salt and iridium salt.
• a photographic light-sensitive material mainly comprising silver chloride often shows elution of silver. Further, the smaller the grain diameter of silver halide grains (fine particles), the more frequent is the elution of silver. Thus, a photographic light-sensitive material comprising silver chloride fine grains shows elution of silver quite frequently.
• the interaction of silver with sulfites in the developer causes elution of a large amount of silver complexes in the developer.
• the silver complexes eluted in the developer are reduced by a developing agent to produce silver which then attaches to and accumulates on the development tank, roller, etc. This is called silver stain or silver sludge which can attach to the photographic light-sensitive material being processed, causing stain on the images.
• the developing apparatus requires regular cleaning and maintenance.
• JP-A As used herein means an "unexamined published Japanese patent application”
• JP-B-56-46585 (the term "JP-B” as used herein means an "examined Japanese patent publication") and JP-B-62-28495 disclose another method for reducing silver sludging by adding selected compounds.
• the compounds described therein have an improved anti-sludging function, but they are not necessarily stable and would immediately lose their activity in the system where the developer is subjected to air oxidation. There is a need for a further improvement.
• JP-B-60-24464 utilizes mercaptopyrimidine compounds in bleach-fixing solution for promoting bleaching action.
• German Patent 2126297 utilizes mercaptopyrimidine compounds in the second developer of a color reversal system for the purpose of increasing the sensitivity thereof.
• Exemplary is 2-mercapto-4-hydroxy-6-methylpyrimidine. Evaluating this compound, the inventors found that it is effective for preventing silver sludge from depositing, but to a less extent. Three is a need for a further improvement.
• U.S. Patent 3,597,199 utilizes mercaptopyrimidine derivatives in the second developer of a color reversal system for the purpose of improving photographic properties.
• exemplary is 2-mercapto-4-hydroxy-6-aminopyrimidine. Evaluating this compound, the inventors found that it does not have a satisfactory function of preventing silver sludge.
• JP-A-59-204037 utilizes heterocyclic mercapto compounds in black-and-white developer at pH 11.5 or higher for the purpose of preventing silver sludging.
• One exemplified compound is 2-mercapto-4-hydroxypyrimidine. Testing this compound, we found that it is not necessarily effective for preventing silver sludging.
• JP-B-48-35493 utilizes heterocyclic mercapto compounds in developers for preventing silver sludging.
• exemplary is 2-mercapto-4-hydroxy-6-methylpyrimidine. It is effective for preventing silver sludge from depositing to a less extent as mentioned above.
• UK Patent 1,296,161 uses mercaptopyrimidine derivatives in developers of the silver salt diffusion transfer type for the purpose of preventing silver sludging.
• Exemplary is 2-mercapto-4-hydroxy-6-carboxyquinazoline. Evaluating this compound, the inventors found that it does not have a satisfactory function of preventing silver sludge.
• JP-B-64-121854 discloses a black-and-white developer which contains an amino or heterocyclic compound having a group capable of adsorbing silver halide for achieving improved photographic quality and preventing black pepper.
• JP-B-60-24464 uses a mercaptotriazine in a bleach-fixer for promoting bleaching.
• JP-A-49-5334 adds a heterocyclic mercapto compound to a lith developer to thereby remove trailing of photographic high contrast photosensitive material.
• Exemplary is 2,4,6-trimercapto-1,3,6-triazine.
• JP-A-59-204037 discloses a black-and-white developer at pH 11.5 or higher which contains a heterocyclic mercapto compound, for example, 2,4-dimercapto-6-hydroxy-1,3,5-triazine for preventing silver sludge.
• JP-A-3-53244 uses mercapto-1,3,5-triazine in a developer for preventing silver sludge.
• An example is 2,4-dimercapto-6-hydroxy-1,3,5-triazine again. Evaluating these compounds, we found that they do not have a satisfactory function of preventing silver sludge.
• One prior art well-known image toner is 1-phenyl-5-mercaptotetrazole (see T.H. James, The Theory of the Photographic Process , Ch. 16, page 476) which greatly affects photographic properties such as fog, sensitivity and gradation. There is a desire for a method capable of approximating yellow brown color tone to completely neutral with minimal influence on photographic properties.
• a method for processing a silver halide photographic material comprising a support and at least one hydrophilic colloidal layer including at least one light-sensitive silver halide emulsion layer, which comprises processing the silver halide photographic material which has been exposed to light with a developer containing a compound represented by the following general formula (I) by means of an automatic developing machine with a development tank having an opening ratio of 0.05 or less: wherein R1 and R2 each represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a hydroxyl group, -SM, -COOM, -SO3M, -PO(OM)2 (wherein M represents a hydrogen atom, an alkali metal atom or an ammonium group), an amino group, a nitro group, a cyano group, a halogen atom, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a
• a silver halide photographic material comprising a support and at least one hydrophilic colloidal layer comprising at least one light-sensitive silver halide emulsion layer containing a silver halide grains having a silver chloride content of 90 mol% or more and having an average grain diameter of 0.25 ⁇ m or less is processed with a developer containing the compound represented by the general formula (I).
• the photographic light-sensitive material can exert its effects remarkably when ultrahigh contrast is required.
• Examples of an alkali metal atom include Na and K, and examples of a halogen atom include F, Cl, Br and I.
• Examples of the cyclic group formed with R1 and R2 include a hydrocarbon ring preferably having 5 to carbon atoms and a heterocyclic group preferably a 5 to 6 membered heterocyclic group containing at least one of N, O, and S atoms as a hetero atom.
• An alkyl group, an aryl group, an aralkyl group, an amino group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfamoyl group, and an alkoxy group represented by R1 or R2, and the cyclic group formed with R1 and R2 may be substituted with at least one of substituents such as the groups represented by R1 or R2 and a heterocyclic group preferably a 5 to 6 membered heterocyclic group containing at least one of N, O, and S atoms as a hetero atom, and these substituted groups may be further substituted with at least one of the substituents.
• R1 or R2 is a C1 ⁇ 10 alkyl group (i.e., an alkyl group containing from 1 to 10 carbon atoms) which may contain at least one substituent (in the present invention the carbon number includes also that of the substituent(s)), a C6 ⁇ 12 aryl group which may contain at least one substituent, a C7 ⁇ 12 aralkyl group which may contain at least one substituent, a nitro group, a cyano group or a halogen atom.
• the sum of the carbon atoms contained in R1 and R2 is preferably in the range of 2 to 20.
• R1 and R2 are connected to each other to form a saturated 5- or 6-membered ring.
• R1 is a hydrogen atom or an alkyl group containing at least one amino group or heterocyclic group (e.g., morpholino, piperadinyl and pyrrolidinyl) as a substituent
• R2 is a C1 ⁇ 10 alkyl group which may contain at least one substituent or a C6 ⁇ 12 aryl group which may contain substituents.
• a saturated 5- or 6-membered ring (e.g., a 5- or 6-membered hydrocarbon ring) formed by connecting R1 and R2 to each other is also preferred.
• R1 examples include a dimethylaminomethyl group, a morpholinomethyl group, an N-methylpiperadinylmethyl group, and a pyrrolidinylmethyl group.
• R2 examples include a methyl group, an ethyl group, a phenyl group, and a p-methoxyphenyl group.
• the amount of the compound of the present invention to be added to the developer is preferably in the range of 0.01 to 100 mmol, more preferably 0.1 to 10 mmol per l of developer. When the amount exceeds 100 mmol, development restraining action tends to increase, and some of the compounds is difficult to dissolve into the developer.
• the opening ratio of the development tank zone in the automatic developing machine is particularly preferably in the range of 0.04 to 0.001.
• a floating lid or a cover is provided on the whole surface of a processing solution, and the floating lid or the cover is removed only when the photographic material passes through the solution, or a floating lid or a cover is provided on the solution where the photographic material does not pass through and on the solution where a transporting apparatus is not provided.
• the photographic light-sensitive material to be used in the present invention is particularly preferably in the form of a sheet having a width of 0.3 to 1.2 m.
• the silver halide emulsion to be used in the present invention is a dispersion of silver halide such as silver chloride, silver iodide, silver bromide, silver bromochloride, silver bromoiodide and silver bromochloroiodide in a hydrophilic colloid.
• the silver halide emulsion is prepared by mixing a water-soluble silver salt (e.g., silver nitrate) and a water-soluble halogen salt in the presence of water and a hydrophilic colloid in accordance with a method well known in the art (e.g., single jet process, double jet process, controlled jet process), and then subjecting the material to physical ripening and chemical ripening such as gold sensitization and/or sulfur sensitization.
• a method well known in the art e.g., single jet process, double jet process, controlled jet process
• the shape of silver halide grains to be used in the present invention is not specifically limited. Any of cubic grains, octahedral grains and spheric grains can be used. Further, tabular silver halide grains with a high aspect ratio as disclosed in Research Disclosure No. 22534 (January 1983) can be used.
• silver halide emulsions are preferably used.
• silver bromide or silver bromoiodide is preferred.
• Such a silver halide emulsion preferably has a silver iodide content of 10 mol% or less, particularly 0 to 5 mol%.
• Such a silver halide emulsion provides a high sensitivity and is adapted for rapid processing.
• the tabular silver halide emulsion is preferably in the form of tablet having an aspect ratio of 4 to 20, more preferably 5 to 10 and a thickness of 0.3 ⁇ m or less, more preferably 0.2 ⁇ m or less.
• the aspect ratio of tabular silver halide emulsion is given by the ratio of the average value of the diameter of circles having the same area as the projected area of individual tabular grains to the average value of the thickness of individual tabular grains.
• Tabular grains are preferably present in a proportion of 80% by weight or more, more preferably 90% by weight or more, of all grains in the tabular silver halide emulsion.
• the stability of photographic properties given upon the running processing of the present invention can be further enhanced. Further, since the coated amount of silver can be reduced, the load in the fixing and drying procedures can be reduced. This also enables rapid processing.
• the tabular silver halide emulsion can also be prepared by forming seed crystals containing 40 weight% of tabular grains at an atmosphere of pBr 1.3, and then adding a silver and halogen solutions into the system while keeping the pBr at the same degree to grow up the seed crystals.
• the size of the tabular silver halide grains can be controlled by controlling the temperature, properly selecting the type and the amount of the solvent, and controlling the addition rate of the silver salt and the halide upon the growth of the grains.
• the silver halide emulsion used in the present invention may be a polydispersed emulsion.
• the monodispersed emulsion having a distribution coefficient (which represents the grain distribution) of 20% or less is preferably used in a photographic material for printing.
• a monodispersed emulsion means an emulsion which has grain size distribution of 20% or less, especially preferably 15% or less as a fluctuation coefficient.
• the silver halide grain may comprise an inner portion and a surface layer which may be a uniform or different phases. A mixture of two of more silver halide emulsions which are prepared separately may be used.
• the silver halide grains may be grains in which a latent image is formed mainly on the surface thereof or grains in which a latent image is formed mainly thereinside.
• the silver halide grains may be grains which have been previously fogged on the surface thereof.
• the effects of the present invention can be obtained when the photographic material having at least one light-sensitive silver halide emulsion layer comprising silver chloride or silver bromochloride containing silver chloride in an amount of 90 mol% or more, preferably 95 mol% or more is developed with the developer of the present invention.
• the effect of the present invention is more remarkable when the development tank having an opening ratio of 0.05 or less is used.
• Such a silver halide emulsion is preferably obtained by the formation of silver halide grains in the presence of a water-soluble rhodium salt in an amount of 1 ⁇ 10 ⁇ 7 mol to 5 ⁇ 10 ⁇ 4 mol, preferably 1 ⁇ 10 ⁇ 6 mol to 1 ⁇ 10 ⁇ 4 mol, per mol of silver.
• rhodium salt examples include rhodium trichloride, ammonium hexachlororhodiumate(III), aqua-complex of ammonium pentachlororhodiumate(III), and potassium hexachlororhodiumate(III). If the added amount of rhodium salt falls below 10 ⁇ 7 mol, in some cases the safelight safety is not sufficiently obtained. If the added amount of rhodium salt exceeds 5 ⁇ 10 ⁇ 4 mol, sensitivity is too low, and the rise in contrast by the addition of a hydrazine derivative or tetrazolium compound can hardly occur.
• the average grain size of such a silver halide emulsion is preferably 0.25 to 0.03 ⁇ m, more preferably 0.20 to 0.05 ⁇ m.
• the grain size distribution of the silver halide emulsion is preferably monodisperse. In such a silver halide emulsion, 90% or more of all the grains fall within a range between ⁇ 40%, preferably ⁇ 20%, from the average grain diameter.
• the silver halide grains in such an emulsion preferably have a regular crystal form such as cube and octahedron, but may have an irregular crystal form such as sphere and tablet or a composite thereof.
• the reaction of a water-soluble silver salt (aqueous solution of silver nitrate) and a water-soluble halogen salt may be accomplished by a single jet method, a double jet method or a combination thereof.
• a double jet method is one in which the pAg value of the liquid phase in which silver halide is formed is kept constant, i.e., a controlled double jet method can be used.
• a so-called silver halide solvent such as ammonia, thioether and tetra-substituted thiourea can be used to form grains.
• the above mentioned controlled double jet method and the grain formation method using a silver halide solvent are effective to prepare a silver halide emulsion having a regular crystal form and a narrow grain size distribution.
• a silver halide emulsion which has not been subjected to chemical sensitization is preferably used.
• the silver halide emulsion layer of the photographic material used in the present invention may comprise at least two kinds of silver halide emulsions having different sensitivities.
• the requirements for high contrast include a configuration in which the sensitivity of a lower emulsion layer is higher than that of an upper emulsion layer.
• the difference in sensitivity between the lower emulsion layer and the upper emulsion layer adjacent thereto is in the range of 0.05 log E to 0.5 log E, preferably 0.1 log E to 0.4 log E (wherein log E represents exposure).
• the sensitivity of the various emulsion layers can be each determined by developing each of the various layers in the form of single layer.
• silver halide emulsion layers having different sensitivities can be prepared by varying the rhodium content, halogen composition, grain size, etc. of the silver halide grains used, or by incorporating in the emulsion an additive which is adsorbed to silver halide grains to change the sensitivity thereof (e.g., fog inhibitor).
• an additive which is adsorbed to silver halide grains to change the sensitivity thereof (e.g., fog inhibitor).
• a hydrazine derivative or tetrazolium compound may be incorporated into the photographic light-sensitive material for the purpose of providing an ultrahigh contrast.
• a cadmium salt, sulfite, lead salt, thallium salt, rhodium salt or complex salt thereof, iridium salt or complex salt thereof or the like may be present in the system.
• an iridium salt is preferably present in the system in an amount of 10 ⁇ 8 to 10 ⁇ 3 mol per mol of silver halide to prepare the silver halide emulsion of the present invention.
• the silver halide emulsion of the present invention may be an emulsion containing at least one iron, rhenium, ruthenium or osmium compound.
• the amount of such a compound to be added is in the range of 10 ⁇ 3 mol or less, preferably 10 ⁇ 6 to 10 ⁇ 4 mol per mol of silver.
• the emulsion of the present invention may or may not be chemically sensitized.
• the chemical sensitization method can be one of the known chemical sensitization methods such as sulfur sensitization, reduction sensitization and gold sensitization, singly or in combination. Preferred among these chemical sensitization methods is the sulfur sensitization method.
• the sulfur sensitizers can be sulfur compounds contained in gelatin as well as various sulfur compounds such as thiosulfate, thiourea, thiazole and rhodanine. Specific examples of such sulfur compounds are disclosed in U.S. Patents 1,574,944, 2,278,947, 2,410,689, 2,728,668, 3,501,313, and 3,656,955. Preferred sulfur compounds are thiosulfates and thiourea compounds.
• the pAg value during the chemical sensitization procedure is preferably in the range of 8.3 or less, more preferably 7.3 to 8.0.
• Typical of the noble metal sensitization methods is gold sensitization method, which uses a gold compound, particularly a gold complex.
• Complex salts of noble metals other than gold, such as platinum, palladium and iridium may be included. Specific examples of such compounds are disclosed in U.S. Patent 2,448,060 and British Patent 618,061.
• the reduction sensitizers can be stannous salts, amines, sulfinoformamidine, dialkylaminoborane, silane compounds, etc. Specific examples of these reduction sensitizers are disclosed in U.S. Patents 2,487,850, 2,518,698, 2,983,609, 2,983,610, and 2,694,637.
• the silver halide grains to be used in the present invention are preferably subjected to spectral sensitization with a sensitizing dye.
• Examples of such a sensitizing dye include cyanine dye, merocyanine dye, composite cyanine dye, composite merocyanine dye, holopolar cyanine dye, hemicyanine dye, styryl dye, and hemioxonol dye. Particularly useful among these dyes are cyanine dye, merocyanine dye, and composite merocyanine dye. Any of the nuclei commonly used for cyanine dyes as basic heterocyclic nuclei can be applied to these dyes.
• carbocyanine sensitizing dyes are preferred. Specifically, those described in Research Disclosure No. 17643 (December 1978), vol. 170, page 23, and U.S. Patents 4,425,425, and 4,425,426 may be used.
• the time at which the sensitizing dye is added to the emulsion is normally before the coating of the emulsion on a proper support but may be during the chemical ripening procedure or the silver halide grain formation procedure.
• the emulsion layer in the photographic light-sensitive material of the present invention may comprise a plasticizer such as a polymer (e.g., alkyl acrylate latex), an emulsified compound and a polyol (e.g., trimethylol propane) to improve its pressure properties.
• a plasticizer such as a polymer (e.g., alkyl acrylate latex), an emulsified compound and a polyol (e.g., trimethylol propane) to improve its pressure properties.
• the photographic emulsion layer or other hydrophilic colloidal layers in the light-sensitive material may comprise various surface active agents for the purpose of facilitating coating and emulsion dispersion inhibiting electrification and adhesion, and improving slipperiness and photographic properties (e.g., accelerating development, improving contrast, sensitization).
• surface active agents include nonionic surface active agents such as saponin (steroid series), alkylene oxide derivatives (e.g., polyethylene glycol, polyethylene glycol/polypropylene glycol condensate, polyethylene glycol alkyl ether or polyethylene glycol alkylaryl ether, polyethylene glycol ester, polyethylene glycol sorbitan ester, polyalkylene glycol alkylamine or amide, polyethylene oxide addition product of silicone), glycidol derivatives (e.g., alkenylsuccinic acid polyglyceride, alkylphenol polyglyceride), aliphatic esters of polyvalent alcohols, or alkyl esters of saccharides, anionic surface active agents containing acid groups such as a carboxyl group, a sulfo group, a phospho group, an ester sulfate group or an ester phosphate group (e.g., alkylcarboxylate, alkylsulfonate, alkyl
• the silver halide photographic material to be used in the present invention comprises at least one silver halide emulsion layer on a support. If it is used as a direct medical X-ray light-sensitive material, it preferably comprises at least one silver halide emulsion layer on both sides of the support as described in JP-A-58-127921, JP-A-59-90841, JP-A-58-111934, and JP-A-61-201235.
• the photographic light-sensitive material of the present invention may further comprise an interlayer, a filter layer, an anti-halation layer, etc. as necessary.
• the amount of silver to be incorporated into the photographic light-sensitive material to be used in the present invention is preferably in the range of 0.5 g/m2 to 5 g/m2 (one side), more preferably 1 g/m2 to 4 g/m2 (one side).
• this value preferably falls below 5 g/m2. Further, in order to provide a constant image density and contrast, this value preferably exceeds 0.5 g/m2.
• the binder or protective colloid to be incorporated into the hydrophilic emulsion may be gelatin.
• Other hydrophilic colloids may also be used.
• hydrophilic colloids which can be used in the present invention include protein such as gelatin derivatives, graft polymer of gelatin with other high molecular compounds, albumine, and casein, cellulose derivative such as hydroxyethyl cellulose, carboxymethyl cellulose, a cellulose ester sulfate, sodium alginate, and a saccharide derivative such as a starch derivative, a homopolymer or a copolymer such as a polyvinyl alcohol, and other various synthetic hydrophilic high molecular compounds such as a polyvinyl alcohol partial acetal, a poly-N-vinyl pyrrolidone, a polyacrylic acid, a polymethacrylic acid, a polyacrylamide, a polyvinyl imidazole, and a polyvinyl pyrazole.
• the gelatin may be lime-treated gelatin, as well as acid-treated gelatin. Furthermore, hydrolyzate of gelatin and an enzymatic decomposition product of gelatin can be used.
• the emulsion or other hydrophilic colloidal layers particularly in X-ray light-sensitive materials preferably comprise an organic substance which elutes during a development processing in order to reduce the drying load.
• a substance is a gelatin, it is preferably a gelatin which does not undergo a crosslinking reaction by a film hardener, such as acetylated gelatin and phthalated gelatin.
• the molecular weight of such a gelatin is preferably small.
• high molecular compounds other than gelatin that can be effectively used are polyacrylamides as disclosed in U.S. Patent 3,271,158, or hydrophilic polymers such as a polyvinyl alcohol and a polyvinyl pyrrolidone.
• Saccharides such as dextran, saccharose and pullulan are also effective.
• Preferred among these high molecular compounds are polyacrylamide and dextran, particularly polyacrylamide.
• the average molecular weight of such a high molecular compound is preferably in the range of 20,000 or less, more preferably 10,000 or less.
• the effective amount of such an organic substance to be eluted upon processing is in the range from 10% to 50%, preferably from 15% to 30%, based on the total weight of the organic substance coated other than the silver halide grains.
• the layer which contains an organic substance that elutes upon processing in the present invention may be either an emulsion layer or a surface protective layer. If the total coated amount of the organic substance is the same, the organic substance is preferably incorporated into both the surface protective layer and the emulsion layer, more preferably the surface protective layer alone, rather than the emulsion layer alone. In photographic light-sensitive materials comprising an emulsion layer having a multi-layer structure, if the total coated amount of the organic substance is the same, the organic substance is preferably incorporated into an emulsion layer nearer to the surface protective layer.
• a matting agent there may be used finely divided grains of an organic compound such as a homopolymer of methyl methacrylate, a copolymer of methyl methacrylate and methacrylic acid and a starch or an inorganic compound such as silica, titanium dioxide and strontium barium sulfate as disclosed in U.S. Patents 2,992,101, 2,701,245, 4,142,894 and 4,396,706.
• the grain size of such a matting agent is preferably in the range of 1.0 to 10 ⁇ m, particularly 2 to 5 ⁇ m.
• the photographic emulsion layer or other layers may be colored with a dye for the purpose of absorbing light in a specified wavelength range, i.e., controlling the spectral composition of light to be incident upon the photographic emulsion layer by providing a halation layer, an irradiation layer or a filter layer.
• a halation layer i.e., an irradiation layer or a filter layer.
• an emulsion for the purpose of crossover cut may be provided under the emulsion layer.
• Such a dye examples include oxonol dye, azo dye, azomethine dye, anthraquinone dye, arylidene dye, styryl dye, triarylmethane dye, merocyanine dye and cyanine dye containing a pyrazolone nucleus or a barbituric acid nucleus.
• the layer to be mordanted with such a dye using a polymer having a cation site may be an emulsion layer, a surface protective layer, or the side of the support opposite the emulsion layer, preferably a layer between the emulsion layer and the support, ideally a layer in a subbing layer particularly for the purpose of cutting crossover in medical X-ray double-sided film.
• a coating aid for the subbing layer there may be preferably used a polyethylene oxide nonionic surface active agent in combination with a polymer having a cation site.
• the polymer having a cation site is preferably an anion-exchanged polymer.
• the anion-exchanged polymers can be various known quaternary ammonium salt (or phosphonium salt) polymers. These quaternary ammonium salt (or phosphonium salt) polymers are widely known as mordant polymers or antistatic polymers in the following publications.
• mordant polymers or antistatic polymers include water-dispersed latexes as disclosed in JP-A-59-166940, JP-A-55-142339, JP-A-54-126027, JP-A-54-155835, JP-A-53-30328, and JP-A-54-92274, and U.S. Patent 3,958,995, polyvinyl pyridinium salts as disclosed in U.S. Patents 2,548,564, 3,148,061, and 3,756,814, water-soluble quaternary ammonium salt polymers as described in U.S. Patent 3,709,690, and water-insoluble quaternary ammonium salt polymers as described in U.S. Patent 3,898,088.
• quaternary ammonium salt (or phosphonium salt) polymers are particularly preferably used in the form of an aqueous polymer latex obtained by copolymerizing and crosslinking monomers containing at least two or more (preferably 2 to 4) ethylenically unsaturated groups so that the polymers can be prevented from moving from the desired layer to other layers or processing solutions to exhibit photographically undesirable effects.
• the photographic light-sensitive material to be used in the present invention may be designed to exhibit ultrahigh contrast photographic properties by using a hydrazine nucleating agent.
• This system and the hydrazine nucleating agent to be used therein are described in the following references. This system is preferably used particularly for graphic arts. Research Disclosure Item 23516 (p. 346, November 1983) and references cited therein, U.S.
• the silver halide emulsion layer preferably comprises a hydrazine derivative represented by the following general formula (II) for the purpose of providing a high contrast: wherein A represents an aliphatic group, an alicyclic group, or an aromatic group; B represents a formyl group, an acyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkylsulfinyl group, an arylsulfinyl group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfinamoyl group, an alkoxysulfonyl group, a thioacyl group, a thiocarbamoyl group, a sulfanyl group (e.g., an alkylthio group an arylthio group) or heterocyclic group; and each of R
• the aliphatic and alicyclic group represented by A is preferably a C1 ⁇ 30, particularly a C4 ⁇ 20 straight-chain, branched or cyclic alkyl group.
• the branched alkyl group may be cyclized so as to form a heterocyclic group containing one or more hetero atoms, for example, a 4- to 8-membered heterocyclic group containing at least one of N, O and S atoms as a hetero atom.
• the alkyl group may contain substituents such as an aryl group, an alkoxy group, a sulfoxy group (e,g., alkyl- and aryl-sulfoxy group), a sulfonamido group (e.g., alkyl- and aryl-sulfonamido group) and an acylamino group (e,g., aliphatic- and aromatic-acylamino group).
• substituents such as an aryl group, an alkoxy group, a sulfoxy group (e,g., alkyl- and aryl-sulfoxy group), a sulfonamido group (e.g., alkyl- and aryl-sulfonamido group) and an acylamino group (e,g., aliphatic- and aromatic-acylamino group).
• alkyl group examples include a t-butyl group, an n-octyl group, a t-octyl group, a cyclohexyl group, a pyrrolidyl group, an imidazolyl group, a tetrahydrofuryl group, and a morpholino group.
• the aromatic group represented by A is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group.
• a preferred heterocyclic group is a 4- to 8-membered heterocyclic group containing at least one of N, O and S atoms as a hetero atom.
• the unsaturated heterocyclic group may be connected to a monocyclic or bicyclic aryl group to form a heteroaryl group.
• Examples of such a group include benzene ring, a naphthalene ring, a pyridine ring, a pyrimidine ring, an imidazole ring, a pyrazole ring, a quinoline ring, an isoquinoline ring, a benzimidazole ring, a thiazole ring, and a benzothiazole ring.
• Preferred among these aromatic groups are those containing a benzene ring.
• a particularly preferred example of the aromatic group represented by A is an aryl group.
• the aryl group or the unsaturated heterocyclic group represented by A may contain at least one substituent.
• substituents include straight-chain, branched or cyclic alkyl groups (preferably C1 ⁇ 20 alkyl groups), aralkyl groups (preferably monocyclic or bicyclic aralkyl group having an alkyl moiety containing 1 to 3 carbon atoms), alkoxy groups (preferably C1 ⁇ 20 alkoxy groups), substituted amino groups (preferably amino group substituted by C1 ⁇ 20 alkyl groups), acylamino groups (including aliphatic- and aromatic-acyl group; preferably C2 ⁇ 30 acylamino groups), sulfonamido groups (including alkyl- and aryl-sulfonamido group; preferably C1 ⁇ 30 sulfonamido groups), and ureido groups (preferably C1 ⁇ 30).
• the groups represented by A and which are substituted with at least one of the substituents may be further substituted with at least one of the substituents.
• the group represented by A may comprise a ballast group commonly used in an immobile photographic additive such as a coupler.
• a ballast group is a group having 8 or more carbon atoms relatively inert to the photographic properties. It can be selected from the group consisting of alkyl group, alkoxy group, phenyl group, alkylphenyl group, phenoxy group, and alkylphenoxy group.
• the group represented by A may comprise a group which enhances its adsorption to the surface of silver halide grains.
• Examples of such an adsorption group include those disclosed in U.S. Patents 4,385,108, and 4,459,347, JP-A-59-195233, JP-A-59-200231, JP-A-59-201045, JP-A-59-201046, JP-A-59-201047, JP-A-59-201048, and JP-A-59-201049, such as a thiourea group, a heterocyclic thioamido group, a mercapto heterocyclic group and a triazole group.
• Groups represented by B preferably have 1 to 30 carbon atoms and they may be substituted with at least one substituent such as an alkyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group, a cyano group, an alkyl- or aryl-sulfonyl group, an aliphatic- and aromatic-acylamino group and a halogen atom.
• the substituted groups may be further substituted with these substituents.
• B specifically represents a formyl group, an acyl group (such as aliphatic- and aromatic-acyl group, e.g., acetyl, propionyl, trifluoroacetyl, chloroacetyl, benzoyl, 4-chlorobenzoyl, pyruvoyl, methoxallyl, methyloxamoyl), an alkylsulfonyl group (e.g., methanesulfonyl, 2-chloroethanesulfonyl), an arylsulfonyl group (e.g., benzenesulfonyl), an alkylsulfinyl group (e.g., methanesulfinyl), an arylsulfinyl group (e.g., benzenesulfinyl), a carbamoyl group (e.g., methylcarbamoyl, phenylcarbamo
• a formyl group and an acyl group are especially preferable.
• R0 and R1 each represents a hydrogen atom, an alkylsulfonyl or arylsulfonyl group having 20 or less carbon atoms (preferably phenylsulfonyl group or phenylsulfonyl group which is substituted so that the sum of Hammett's substituent becomes -0.5 or more), an acyl group having 20 or less carbon atoms (such as aliphatic- and aromatic-acyl group; preferably benzoyl group or benzoyl group which is substituted so that the sum of Hammett's substituent becomes -0.5 or more); or a straight-chain, branched or cyclic unsubstituted or substituted aliphatic- or alicyclic- acyl group.
• substituents the groups represented by R0 and R1 include halogen atom, ether group, sulfonamido group, carbonamido group, hydroxyl group, carboxyl group, and sulfonic acid group.
• R0 or R1 is a hydrogen atom.
• the hydrazine nucleating agent is to be incorporated into the photographic light-sensitive material, it is preferably incorporated into a silver halide emulsion layer but may be incorporated into other light-insensitive hydrophilic colloidal layers (e.g., protective layer, interlayer, filter layer, antihalation layer).
• the amount of the hydrazine nucleating agent in the silver halide emulsion is preferably in the range of 5 ⁇ 10 ⁇ 7 mol to 5 ⁇ 10 ⁇ 2 mol, more preferably 1 ⁇ 10 ⁇ 6 mol to 2 ⁇ 10 ⁇ 2 mol per mol of silver halide in the same silver halide emulsion layer and in the light-insensitive layer is preferably in the range of 1 ⁇ 10 ⁇ 5 to 5 ⁇ 10 ⁇ 2 mol, more preferably 1x10 ⁇ 4 mol to 2 ⁇ 10 ⁇ 2 mol per mol of silver halide (in the adjacent silver halide emsulsion layer(s)).
• the hydrazine derivative to be used in the present invention when it is to be incorporated into the photographic light-sensitive material, it may be incorporated into a silver halide emulsion or hydrophilic colloidal solution, in the form of aqueous solution, if it is water-soluble, or in the form of solution in an organic solvent miscible with water such as alcohol (e.g., methanol, ethanol), ester (e.g., ethyl acetate) and ketone (e.g., acetone), if it is water-insoluble.
• alcohol e.g., methanol, ethanol
• ester e.g., ethyl acetate
• ketone e.g., acetone
• the addition of the compound may be conducted at any time between the beginning of the chemical ripening of the emulsion and the coating of the emulsion, preferably after the completion of the chemical ripening.
• the compound may be incorporated in a coating solution which has been prepared for coating.
• the development accelerators or nucleation infectious development accelerators suitable for this ultrahigh contrast system may be compounds as disclosed in JP-A-53-77616, JP-A-54-37732, JP-A-53-137133, JP-A-60-140340, and JP-A-60-14959 as well as various compounds containing nitrogen or sulfur atoms.
• the optimum added amount of such an accelerator varies with the kind of the compound used but is normally in the range of 1.0 ⁇ 10 ⁇ 3 to 0.5 g/m2, preferably 5.0 ⁇ 10 ⁇ 3 to 0.1 g/m2.
• a redox compound which releases a development inhibitor may be used in combination with the above mentioned compounds.
• a redox compound can be a compound as disclosed in JP-A-2-293736, and JP-A-2-308239, and Japanese Patent Application No. 1-154060, (corresponding to EP 436027) and JP-A-3-69933 (corresponding to U.S. Patent 5,006,444).
• Such a redox compound may be preferably used in an amount of 1 ⁇ 10 ⁇ 6 to 5 ⁇ 10 ⁇ 2 mol, particularly 1 ⁇ 10 ⁇ 5 to 5 ⁇ 10 ⁇ 2 mol, per mol of silver halide.
• the tetrazolium compound to be used in the present invention can be a compound as disclosed in JP-A-52-18317, JP-A-53-17719, and JP-A-53-17720.
• Typical examples of such a compound include those represented by the following general formulae (III) or (IV): wherein R2 and R3 each represents a group selected from the group consisting of a phenyl group (e.g., phenyl, tolyl, hydroxyphenyl, carboxyphenyl, aminophenyl, mercaptophenyl), a thiazolyl group, a benzothiazolyl group, a pyridyl group, and a triazyl group; and R10, R11, R12 and R13 each represents a phenyl group or a pyridyl group. These groups may all be groups which form a metal chelate or complex.
• R4 represents a group selected from the group consisting of a phenyl group, a heterocyclic group (such as a 5- to 6-membered heterocyclic group containing at least one of N, O and S atoms as a hetero atom, e.g., furyl, thienyl, pyridoyl, quinolyl, benzooxazolyl), an alkyl group (e.g., methyl, ethyl, propyl, butyl, mercaptomethyl, mercaptoethyl), a hydroxyl group, a carboxyl group and salts thereof, an alkoxycarbonyl group (e.g., methoxycarbonyl, ethoxycarbonyl), an amino group (e.g., amino, ethylamino, anilino), mercapto group, nitro group, a hydrogen atom, a cyano group, and an acyl group.
• a heterocyclic group such as
• E represents a group selected from the group consisting of an alkylene group, an arylene group, and an aralkylene group.
• X ⁇ represents an anion.
• the suffix n represents an integer 1 or 2, with the proviso that if the compound forms an intramolecular salt, n is 1.
• the anion moiety can be a high alkylbenzenesulfonic acid anion such as p-dodecylbenzenesulfonic acid anion, a higher alkylsulfuric ester anion such as lauryl sulfate anion, a dialkylsulfoxynate anion such as di-2-ethylhexyl sulfoxynate anion, a polyether alcohol sulfuric ester anion such as cetylpolyethenoxysulfate anion, a high aliphatic anion such as stearic anion, a polymer with an acid group such as polyacrylic anion, etc.
• a high alkylbenzenesulfonic acid anion such as p-dodecylbenzenesulfonic acid anion
• a higher alkylsulfuric ester anion such as lauryl sulfate anion
• a nondiffusive tetrazolium compound of the present invention can be synthesized.
• These nondiffusive tetrazolium compounds may be dispersed in a gelatin matrix by dispersing a soluble salt having the necessary anion moiety and a soluble tetrazolium compound separately in gelatin, and mixing with each other, or crystal of the nondiffusive tetrazolium compound previously synthesized may be dissolved in a suitable solvent (e.g., dimethyl sulfoxide), and then dispersed in a gelatin matrix.
• a suitable solvent e.g., dimethyl sulfoxide
• an ultrasonic wave or a suitable homogenizer such as MANTONGORIN (trade name) homogenizer may be used to make the emulsion dispersion.
• the tetrazolium compound to be used in the present invention can be either a diffusive tetrazolium compound or nondiffusive tetrazolium compound if the high silver chloride-containing emulsion described hereinbefore is used. If a non-diffusive tetrazolium compound is used, an image with a higher contrast can be obtained. Accordingly, if excellent dot properties are particularly required, a nondiffusive tetrazolium compound is relatively advantageously used.
• Tetrazolium compounds may be used singly or in combination.
• the amount of the tetrazolium compound to be used in the present invention is preferably in the range of 1 ⁇ 10 ⁇ 3 to 5 ⁇ 10 ⁇ 2 mol per mol of silver halide. If the amount exceeds 1 ⁇ 10 ⁇ 3 mol per mol of silver halide the development restraining effect tends to be overmuch.
• the photographic light-sensitive material of the present invention may comprise various compounds for the purpose of inhibiting fogging during the preparation, storage or photographic processing of light-sensitive material or for stabilizing photographic properties.
• these fog inhibitors or stabilizers include azoles such as benzothiazolium salt, nitroindazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptotetrazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, aminotriazoles, benzothiazoles and nitrobenzotriazoles, mercaptotriazines, thioketo compounds such as oxazolinethione, azaindenes such as triazaindenes, tetraazaindenes (particularly 4-hydroxy-substituted (1,3,3a,7)-tetraazaindenes), and pentaazaindenes, benz
• benzotriazoles e.g., 5-methyl-benzotriazole
• nitroindazoles e.g., 5-nitroindazole
• JP-A-62-30243 A compound which releases an inhibitor during development as disclosed in JP-A-62-30243 can be incorporated into the processing solution as a stabilizer or for the purpose of inhibiting black pepper.
• the photographic light-sensitive material used in the present invention may comprise a developing agent such as a hydroquinone derivative and a phenidone derivative for various purposes such as a stabilizer or an accelerator.
• a developing agent such as a hydroquinone derivative and a phenidone derivative for various purposes such as a stabilizer or an accelerator.
• the photographic light-sensitive material may contain an inorganic or organic film hardener in the photographic emulsion layer or other hydrophilic colloidal layers.
• chromium salts e.g., chromium alum, chromium acetate
• aldehydes e.g., formaldehyde, glutaraldehyde
• N-methylol compounds e.g., dimethylolurea
• dioxane derivatives e.g., activated vinyl compounds (e.g., 1,3,5-triacryloylhexahydro-s-triazine, 1,3-vinylsulfonyl-2-propanol), activated halogen compounds (e.g., 2,4-dichloro-6-hydroxy-s-triazine), and mucohalogenic acids (e.g., mucochloric acid) may be used singly or in combination.
• chromium salts e.g., chromium a
• the photographic light-sensitive material may comprise a hydroquinone derivative which releases a development inhibitor in response to the image density upon development (so-called DIR-hydroquinone) in the photographic emulsion layer or other hydrophilic colloidal layers.
• a hydroquinone derivative which releases a development inhibitor in response to the image density upon development (so-called DIR-hydroquinone) in the photographic emulsion layer or other hydrophilic colloidal layers.
• hydroquinone derivatives include compounds as disclosed in U.S. Patents 3,379,529, 3,620,746, 4,377,634, and 4,332,878, and JP-A-49-129536, JP-A-54-67419, JP-A-56-153336, JP-A-56-153342, JP-A-59-278853, JP-A-59-90435, JP-A-59-90436, and JP-A-59-138808.
• the photographic light-sensitive material to be used in the present invention may comprise a dispersion of a water-insoluble or difficultly water-soluble synthetic polymer for the purpose of dimensional stability.
• a polymer comprising as a monomer component alkyl (meth)acrylate, alkoxyacryl (meth)acrylate, glycidyl (meth)acrylate, etc., singly or in combination, or a combination thereof with acrylic acid, methacrylic acid, etc., may be used.
• the photographic light-sensitive material of the present invention may preferably comprise a compound containing an acid group in the silver halide emulsion layer and other layers.
• a compound containing an acid group include organic acids such as salicylic acid, acetic acid and ascorbic acid and polymers or copolymers containing acid monomers such as acrylic acid, maleic acid and phthalic acid as repeating units.
• organic acids such as salicylic acid, acetic acid and ascorbic acid
• acid monomers such as acrylic acid, maleic acid and phthalic acid as repeating units.
• JP-A-61-223834, JP-A-61-228437, JP-A-62-25745, and JP-A-62-55642 for these compounds, reference can be made to JP-A-61-223834, JP-A-61-228437, JP-A-62-25745, and JP-A-62-55642.
• ascorbic acid as a low molecular compound and a water-dispersible latex of a copolymer comprising an acid monomer such as acrylic acid and a crosslinkable monomer having two or more unsaturated groups such as divinylbenzene as a high molecular compound.
• the silver halide emulsion thus prepared may be coated on a support such as cellulose acetate film and polyethylene terephthalate film by a dip coating method, an air knife coating method, a bead coating method, an extrusion doctor coating method, a double coating method, etc., and then dried.
• a support such as cellulose acetate film and polyethylene terephthalate film by a dip coating method, an air knife coating method, a bead coating method, an extrusion doctor coating method, a double coating method, etc.
• the developer for use in the development of the photographic light-sensitive material according to the present invention may contain commonly used additives (e.g., developing agent, alkali agent, pH buffer, preservative, chelating agent).
• the development according to the present invention may be accomplished by any of known methods.
• the developer of the present invention may be any known developer.
• Developing agents to be incorporated into the developer to be used in the present invention are not specifically limited. Dihydroxybenzenes are preferably used. Further, a combination of dihydroxybenzene and 1-phenyl-3-pyrazolidone or a combination of dihydroxybenzene and p-aminophenol is preferably used in view of developability of a black-and-white photographic material.
• the dihydroxybenzene developing agents to be used in the present invention can be hydroquinone, chlorohydroquinone, isopropylhydroquinone, methylhydroquinone, etc. Particularly preferred among these dihydroxybenzene developing agents is hydroquinone.
• Examples of 1-phenyl-3-pyrazolidone or derivatives thereof to be used in the present invention include 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, and 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone.
• Examples of p-aminophenol developing agents to be used in the present invention include N-methyl-p-aminophenol, p-aminophenol, N-( ⁇ -hydroxyethyl)-p-aminophenol, and N-(4-hydroxyphenyl)glycine. Particularly preferred among these p-aminophenol developing agents is N-methyl-p-aminophenol.
• Such a dihydroxybenzene developing agent is preferably used in an amount of 0.05 mol/l to 0.8 mol/l. If such a dihydroxybenzene is used in combination with a 1-phenyl-3-pyrazolidone or a p-aminophenol, it is preferably used in an amount of 0.05 mol/l to 0.5 mol/l and 0.06 mol/l or less, respectively.
• Examples of the preservative to be used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, and an adduct of sodium bisulfite and formaldehyde.
• a sulfite may be used in an amount of 0.20 mol/l or more, particularly 0.3 mol/l or more. However, if too much of such a sulfite is used, it is precipitated in the developer, causing stain in the solution. Accordingly, the upper limit of the amount of the sulfite to be added is preferably 1.2 mol/l.
• an ordinary water-soluble inorganic alkaline metal salt e.g., sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate.
• additives which can be used other than the above mentioned additives include development inhibitors such as sodium bromide and potassium bromide, organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol and dimethyl formamide, development accelerators such as an alkanolamine (e.g., diethanolamine, triethanolamine), imidazole and derivatives thereof, and fog inhibitors or black pepper inhibitors such as an indazole compound (e.g., 5-nitroindazole) and benzotriazole compound.
• a toner, a surface active agent, an anti-foaming agent, a water softener, a film hardener, etc. may be contained in the developer.
• the uneven development inhibitor can be a compound as described in JP-A-62-212651.
• As a dissolution aid there can be used a compound as described in JP-A-61-267759.
• the developer to be used in the present invention may comprise, as a buffer, boric acid as disclosed in JP-A-62-186259, a saccharide (e.g., saccharose), an oxim (e.g., acetoxim), a phenol (e.g., 5-sulfosalicylic acid) or a tertiary phosphate (e.g., sodium salt, potassium salt) as disclosed in JP-A-60-93433, etc.
• Preferred among these buffers is boric acid.
• the pH of the developer is preferably 9.0 to 13.0, and more preferably 9.5 to 12.0.
• the replenishment rate of the developer is preferably not more than 1000 ml per m2, more preferably 60 to 650 ml per m2 of the photographic material to be developed.
• the processing solution is preferably concentrated so that it is diluted before use.
• concentration of the developer it is effective to use a potassium salt as a salt component to be contained in the developer.
• the fixing agent to be incorporated into the fixing solution used in the present invention there may be used, for example, sodium thiosulfate or ammonium thiosulfate. Particularly preferred among these fixing agents is ammonium thiosulfate in light of fixing rate.
• the amount of the known fixing agent to be used can be properly varied and is normally in the range of about 0.1 mol/l to about 2 mol/l.
• the fixing solution may optionally contain a film hardener (e.g., water-soluble aluminum compound), a preservative (e.g., sulfite, bisulfite), a pH buffer (e.g., acetic acid, boric acid), a pH adjustor (e.g., ammonia, sulfuric acid), a chelating agent, a surface active agent, a wetting agent, and a fixing accelerator.
• a film hardener e.g., water-soluble aluminum compound
• a preservative e.g., sulfite, bisulfite
• a pH buffer e.g., acetic acid, boric acid
• a pH adjustor e.g., ammonia, sulfuric acid
• Examples of surface active agent include sulfates, anionic surface active agents such as sulfonate, polyethylene surface active agents, and amphoteric surface active agents as disclosed in JP-A-57-6740. Further, a known anti-foaming agent may be incorporated.
• Examples of the wetting agent include alkanolamine and alkylene glycol.
• Examples of the fixing accelerator include thiourea derivatives and alcohol having a triple bond in its molecule as disclosed in JP-B-45-35754, JP-B-58-122535, and JP-B-58-122536, and thioether compounds as disclosed in U.S. Patent 4,126,459. Further, compounds as disclosed in JP-A-2-44355 may be used.
• the pH buffers can be organic acids such as acetic acid, malic acid, succinic acid, tartaric acid and citric acid or inorganic buffers such as boric acid, phosphate and sulfite. Preferred among these buffers are acetic acid, tartaric acid, boric acid and sulfite.
• the pH buffer is used for the purpose of inhibiting the rise in the pH value of the fixing agent due to the introduction of the developer.
• the amount of the pH buffer to be used is preferably in the range of 0.01 to 1.0 mol/l, more preferably 0.02 to 0.6 mol/l.
• JP-A-64-4739 a compound as disclosed in JP-A-64-4739 may be used.
• Examples of the film hardener to be incorporated into the fixing solution of the present invention include water-soluble aluminum salt and chromium salt. Preferred among these compounds is water-soluble aluminum salt. Examples of such a water-soluble aluminum salt include aluminum chloride, aluminum sulfate, and potassium alum. The amount of such a compound to be added is preferably in the range of 0.01 to 0.2 mol/l, more preferably 0.03 to 0.08 mol/l.
• the fixing temperature and time are preferably in the range of about 20°C to about 50°C and 5 seconds to 1 minute, respectively.
• the replenishment rate of the fixing solution is preferably in the range of 600 ml/m2 or less, particularly 450 ml/m2 or less.
• the photographic light-sensitive material which has been developed and fixed is then rinsed or stabilized.
• the rinse or stabilization can be effected at a replenishment rate of 3 l or less (including 0, that is, water rinse) per m2 of silver halide photographic material.
• the system of the present invention not only enables water-saving processing, but also requires no piping in the automatic developing machine.
• a washing tank with a squeeze roller or crossover roller as disclosed in JP-A-63-18350 and JP-A-62-287252 is preferably provided. Further, in order to lower the pollution load caused when the rinse is conducted with a small amount of water, various oxidizers may be added or filtration may be combined.
• the overflow solution from the washing tank or stabilizing tank caused by the replenishment of mildewproofing water into the washing tank or stabilizing tank in the present invention may be entirely or partially reused for a processing solution having a fixing capacity as its preceding processing step as described in JP-A-60-235133.
• a water-soluble surface active agent or anti-foaming agent may be added.
• a dye adsorbent as described in JP-A-63-163456 may be provided in the washing tank.
• the rinse may be followed by stabilizing.
• a bath containing a compound as described in JP-A-2-201357, JP-A-2-132435, JP-A-1-102553, and JP-A-46-44446 may be used as a final bath for processing the photographic light-sensitive material.
• the stabilizing bath may optionally contain an ammonium compound, a compound of a metal such as Bi and Al, a fluorescent brightening agent, various chelating agents, a film pH adjustor, a film hardener, a germicide, a mildewproofing agent, alkanol amine or a surface active agent.
• the water to be used in the rinse step or stabilizing step may be preferably tap water as well as deionized water or water sterilized by a halogen lamp, ultraviolet germicidal lamp or various oxidizers (e.g., ozone, hydrogen peroxide, chlorate). Further, washing water containing a compound as described in JP-A-4-39652 can be used.
• the development time is in the range of 60 seconds or less, preferably 6 seconds to 30 seconds, and the development temperature is preferably in the range of 25°C to 50°C, more preferably 30°C to 40°C.
• the fixing temperature and time are preferably in the range of about 20°C to about 50°C and 60 seconds or less, more preferably 30°C to 40°C and 6 seconds to 30 seconds, respectively.
• the washing and stabilizing temperatures are preferably in the range of 0 to 50°C.
• the photographic light-sensitive material which has been developed, fixed and washed (or stabilized) is dried usually through a procedure for squeezing the material, i.e., through a squeeze roller.
• the drying is conducted at a temperature of about 40°C to about 100°C, and the drying time can be properly varied depending on the circumstantial conditions.
• Emulsion A Solution 1 Water 1.0 l Gelatin 20 g Sodium chloride 20 g 1,3-Dimethylimidazolidine-2-thione 20 mg Sodium benzenethiosulfonate 8 mg Solution 2 Water 400 ml Silver nitrate 100 g Solution 3 Water 400 ml Sodium chloride 27.1 g Potassium bromide 21 g Potassium hexachloroiridiumate(III) (0.001% aqueous solution) 15 ml Ammonium hexabromorhodiumate (III) (0.001% aqueous solution) 1.5 ml
• Solution 2 and Solution 3 were simultaneously added to Solution 1 which had been kept at a temperature of 38°C and a pH value of 4.5 with stirring over 10 minutes to form nuclear grains having a size of 0.16 ⁇ m.
• Solution 4 and Solution 5 having the following compositions were added to the material over 10 minutes. 0.15 g of potassium iodide was then added to the material to stop the formation of grains.
• Solution 4 Water 400 ml Silver nitrate 100 g Solution 5 Water 400 ml Sodium chloride 27.1 g Potassium bromide 21 g Potassium hexacyanoferrate (III) (0.1% aqueous solution) 5 ml
• the material was then rinsed in accordance with an ordinary flocculation method. 30 g of gelatin was then added to the material.
• the pH value and pAg value of the material were then adjusted to 5.3 and 7.5, respectively.
• the material was then subjected to chemical sensitization at a temperature of 55°C with 2.6 mg of sodium thiosulfate, 1.0 mg of triphenylphosphine selenide, 6.2 mg of chloroauric acid, 4 mg of sodium benzenethiosulfonate and 1 mg of sodium benzenesulfinate to obtain optimum sensitivity.
• the above mentioned emulsion was subjected to ortho sensitization with 5 ⁇ 10 ⁇ 4 mol/mol Ag of an ortho sensitizing dye (compound described below).
• Hydroquinone and 1-phenyl-5-mercaptotetrazole were added to the emulsion as fog inhibitors in an amount of 2.5 g and 50 mg, respectively.
• a polyethyl acrylate latex was added to the emulsion as a plasticizer in a proportion of 25% by weight based on gelatin binder.
• 2-Bis-(vinylsulfonylacetamido)ethane was added to the emulsion as a film hardener.
• colloidal silica was added to the emulsion in a proportion of 40% by weight based on gelatin binder.
• the emulsion was then coated on a polyester support in such an amount that the coated amount of silver and gelatin reached 3.0 g/m2 and 1.0 g/m2, respectively.
• a protective lower layer and a protective upper layer having the following compositions: ⁇ Protective lower layer ⁇ Gelatin 0.25 g/m2 Sodium benzenethiosulfonate 4 mg/m2 1,5-Dihydroxy-2-benzaldoxim 25 mg/m2 Polyethyl acrylate latex 125 mg/m2 (solid content) ⁇ Protective upper layer ⁇ Gelatin 0.25 g/m2 Silica matting agent having an average grain diameter of 2.5 ⁇ m 50 mg/m2 Compound 1 (gelatin dispersion) 30 mg/m2 Colloidal silica having a grain diameter of 10 to 20 m ⁇ m 30 mg/m2 Compound 2 5 mg/m2 Sodium dodecylbenzenesulfonate 22 mg/m2
• the base used in the present example had a back layer and a back protective layer having the following compositions: Sodium dodecylbenzenesulfonate 80 mg/m2 Compound 3 70 mg/m2 Compound 4 85 mg/m2 Compound 5 90 mg/m2 1,3-Divinylsulfone-2-propanol 60 mg/m2
• a coat specimen was prepared as Film B in the same manner as Film A, except that triphenylphosphine selenide used as a chemical sensitizer in the preparation of the emulsion was replaced by triphenylphosphine telluride.
• the composition of the developer is given below.
• Diethylenetriaminepentaacetic acid 2.0 g Sodium carbonate 5.0 g Boric acid 10.0 g Potassium sulfite 85.0 g Sodium bromide 6.0 g
• Diethylene glycol 40.0 g 5-Methylbenzotriazole 0.2 g Sodium 2-mercaptobenzimidazole-5-sulfonate 0.3 g
• Hydroquinone 30.0 g 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 1.6 g Water to make 1 l pH (adjusted with potassium hydroxide) 10.7
• the fixing solution there was used the following composition: Disodium ethylenediaminetetraacetate 0.025 g Sodium sulfite 7.0 g Sodium metabisulfite 20.0 g Sodium thiosulfate pentahydrate 300.0 g Water to make 1 l pH 5.7
• Film A was then exposed to light from a xenon flash lamp having an emission time of 10 ⁇ 6 second through an interference filter having a peak at 488 nm and a continuous wedge.
• opening ratio means an opening ratio in operation (dynamic opening ratio) or opening ratio during suspension (static opening ratio) averaged over the respective allocated time.
• Condition "5" indicates that no silver stain is observed on the film, development tank and roller.
• Condition "1” indicates that silver stain is observed entirely on the film and much silver stain is observed on the roller.
• Condition "4" indicates that no silver stain is observed on the film but a slight amount of silver stain is observed on the development tank and roller.
• Condition "4" is a practically allowable level.
• Condition "3" or below is a level having practical problems or an unallowable level.
• Table 2 shows the results of the photographic properties and silver stain in the running test.
• Comparative Example 2 shows the following facts. As compared with Comparative Example 1, Comparative Example 2, which was conducted at a reduced developer replenishment rate, showed deteriorated photographic properties and silver stain. Comparative Example 3, which was conducted with a lower opening ratio than Comparative Example 2, provided less change in photographic properties but similarly showed much silver stain. As compared with Comparative Example 2, Comparative Example 4, which was conducted with Developer 2 comprising a compound of the present invention, showed less silver stain but similarly showed a bigger change in photographic properties. In Test Nos. 5, 6, 7, and 8, even running tests with Developer Nos. 2, 3, 4 and 5 at a reduced replenishment rate using an automatic developing machine with a reduced opening ratio showed no change in photographic properties nor deterioration in silver stain.
• Film B was subjected to the same test as Film A. As with the results with Film A, it was found that even in running tests with a reduced opening ratio at a reduced replenishment rate, processing with a developer containing a compound of the present invention provides no change in photographic properties and little silver stain.
• the emulsion was then subjected to chemical sensitization with sodium thiosulfate, chloroauric acid and sodium benzenethiosulfonate in an amount of 5 mg, 8 mg and 7 mg, respectively, and the emulsion was heated at a temperature of 60°C for 45 minutes.
• stabilizers there were added 150 mg (per mol of Ag) of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene, and benzoisothiazolone-3 and phenoxyethanol.
• cubic silver bromochloride grains having an average grain size of 0.28 ⁇ m and a silver chloride content of 70 mol% were obtained. (Fluctuation coefficient: 9%)
• Gelatin 1.0 g/m2 1,3-Bisvinylsulfonyl-2-propanol 4.0 wt% based on gelatin
• the light-sensitive emulsion B was redissolved. To the emulsion were then added potassium salt of 5-[3-(4-sulfobutyl)-5-chloro-2-benzoxazolidilidene]-1-hydroxyethoxyethyl-3-(2-pyridyl)-2-thiohydantoin, KI solution, and 1-phenyl-5-mercaptotetrazole in an amount of 1 ⁇ 10 ⁇ 3 mol, 1.0 ⁇ 10 ⁇ 3 mol and 2 ⁇ 10 ⁇ 4 mol per mol of silver, respectively, and 50 mg/m2 of a polyethyl acrylate dispersion, 1,3-bisvinylsulfonyl-2-propanol as a film hardener in an amount of 4.0 wt% based on gelatin, and 1.0 ⁇ 10 ⁇ 4 mol/m2 of a redox compound represented by the following structural formula. The material was then coated in such an amount that the coated amount of silver and gelatin reached 0.2
• a protective layer 1.0 g/m2 of gelatin and 0.3 g/m2 of polymethyl methacrylate grains (average grain diameter: 2.5 ⁇ m) were coated on the material using the following surface active agents:
• the back layer and back protective layer were coated with the following formulations:
• the 1st light-sensitive emulsion layer Onto a polyester film (100 ⁇ m) support was coated the 1st light-sensitive emulsion layer as a lowermost layer. On the lowermost layer were then coated simultaneously the 2nd light-sensitive emulsion layer comprising a redox compound and a protective layer with an interlayer interposed therebetween to prepare Specimen C.
• composition of the developer is given below.
• the composition of the replenisher for the developer has the same composition as this developer.
• Specimen C thus obtained was exposed to light from a tungsten lamp with 3,200°K through an optical wedge for sensitometry, and then processed by means of an automatic developing machine as used in Example 1.
• the development conditions were 34°C and 30".
• the same running test as conducted in Example 1 was conducted.
• the fixing solution was GR-Fl available from Fuji Photo Film Co., Ltd.
• the replenishment rate was 100 ml or 50 ml per full-size specimen.
• Emulsion E was prepared in the same manner as Emulsion D, except that the temperature at which the components were charged into the system was raised to 50°C.
• the average grain size of the resulting cubic silver chloride grains was 0.30 ⁇ m.
• a matting agent sicon dioxide; average grain diameter: 3.5 ⁇ m
• 135 mg/m2 of methanol silica average grain diameter: 0.02 ⁇ m
• 25 mg/m2 of sodium dodecylbenzenesulfonate as a coating aid 20 mg/m2 of sodium salt of sulfuric ester of poly(polymerization degree: 5)oxyethylenenonylphenyl ether, and 3 mg/m2 of potassium salt of N-perfluorooctanesulfonyl-N-propylglycine were simultaneously coated to prepare specimens.
• the base used in the present example had the following back layer and back protective layer. (The percent swelling of the back side was 110%.)
• Emulsion D The specimen prepared from Emulsion D will be hereinafter referred to as "Film D", while the specimen prepared from Emulsion E will be hereinafter referred to as "Film E”.
• the composition of the developer is given below.
• Diethylenetriaminepentaacetic acid 2.0 g Sodium carbonate 5.0 g Boric acid 10.0 g Potassium sulfite 85.0 g Sodium bromide 6.0 g
• Diethylene glycol 40.0 g 5-Methylbenzotriazole 0.2 g Sodium 2-mercaptobenzimidazole-5-sulfonate 0.3 g
• Hydroquinone 30.0 g 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 1.6 g Water to make 1 l pH (adjusted with potassium hydroxide) 10.7
• the fixing solution there was used the following composition: Disodium ethylenediaminetetraacetate 0.025 g Sodium sulfite 7.0 g Sodium metabisulfite 20.0 g Sodium thiosulfate pentahydrate 300.0 g Water to make 1 l pH 5.7
• the specimens thus obtained were each exposed to light through a continuous wedge by means of a Type P-627FM printer (mercury) available from Dainippon Screen Mfg. Co., Ltd.
• the replenishment rate was 50 ml for developer and 100 ml for fixing solution per sheet of full-size specimen.
• the compositions of the replenishing solutions for the developer and the fixing solution were the same as those of the developer and the fixing solution shown hereinabove, respectively.
• Table 6 shows the results of the photographic properties and silver stain in the running test.
• Table 6 shows the following facts. Test Nos. 1 and 2 as comparative example show that Film D, comprising small size grains, shows little change in the photographic properties but shows deteriorated silver stain after the running test. Film E, comprising large size grains, shows little silver stain but shows a great change in the photographic properties (Dmax) which is not allowable. In Test Nos. 3 and 4 with the developer No. 2 comprising the compound of the present invention, Film D (Test No. 3), comprising small size grains, shows little change in the photographic properties and less silver stain. Test Nos. 5, 6 and 7 show similar results as No. 3.
• Emulsion G was prepared in the same manner as Emulsion F, except that the temperature at which the components were charged into the system was raised to 50°C.
• the average grain size of the resulting cubic silver chloride grains was 0.32 ⁇ m.
• Emulsions F and G were added 24 mg/m2 of 5,6-cyclopentane-4-hydroxy-1,3,3a,7-tetrazaindene, 770 mg/m2 (solid content) of an ethyl acrylate latex (average grain diameter: 0.05 ⁇ m), 3 mg/m2 of a compound having the following chemical structure, 126 mg/m2 of 2-bis(vinylsulfonylacetamido)ethane as a film hardener, and 20 mg/m2 of Compound II-7 and 10 mg/m2 of Compound II-24 as hydrazine compounds. These emulsions were each coated on a polyester support in an amount of 2.5 g/m2 as calculated in terms of silver.
• the coating amount of gelatin was 1.7 g/m2.
• On the coat material were then coated 0.8 g/m2 of gelatin, 8 mg/m2 of lipoic acid, 6 mg/m2 of C2H5SO2SNa, and 230 mg/m2 of an ethyl acrylate latex (average grain diameter: 0.05 ⁇ m) as a protective lower layer.
• On this layer were coated 0.7 g/m2 of gelatin and two kinds of dyes having the following chemical structures in the form of solid dispersion as an upper protective layer.
• a matting agent sicon dioxide; average grain diameter: 3.5 ⁇ m
• 135 mg/m2 of methanol silica average grain diameter: 0.02 ⁇ m
• 25 mg/m2 of sodium dodecylbenzenesulfonate as a coating aid 20 mg/m2 of sodium salt of sulfuric ester of poly(polymerization degree: 5)oxyethylenenonylphenyl ether, and 3 mg/m2 of potassium salt of N-perfluorooctanesulfonyl-N-propylglycine were simultaneously coated to prepare Specimens F and G.
• the base used in the present example had the following back layer and back protective layer. (The percent swelling of the back side was 110%.)
• the composition of the developer is given below.
• Specimens F and G thus obtained were each subjected to the same exposure, processing and running tests as conducted in Example 3.
• the replenishment rate of the developer was 75 ml per sheet of full-size specimen.
• the fixing solution was GR-Fl available from Fuji Photo Film Co., Ltd.
• the replenishment rate of the fixing solution was 100 ml per sheet of full-size specimen.
• Table 8 The compositions of the replenishing solutions for the developer and the fixing solution were the same as those of the developer and the fixing solution shown hereinabove, respectively.
• Table 8 shows that silver chloride photographic materials comprising reduced size grains show deteriorated silver stain, while silver chloride photographic materials comprising large size grains show little silver stain but a great change in the photographic properties as in Example 3. Even a silver chloride photographic material comprising reduced size grains can exhibit less silver stain with no change in the photographic properties when processed with a developer containing a compound of the present invention.
• the use of a developer containing a compound of the present invention provides a processing method that allows a silver halide photographic material comprising reduced size grains to show little production of silver in the developer and no silver stain attached to the film with little change in the photographic properties at running conditions.

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• 1993
  • 1993-02-19 DE DE1993602923 patent/DE69302923T2/de not_active Expired - Fee Related
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