Method for processing of silver halide photographic material

Abstract

 A method for processing 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, wherein said silver halide photographic material is exposed and is processed with a developer containing a compound represented by 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, as 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 sulfamoyl group, an aryloxy group, or an alkoxy group, with the proviso that R₁ and R₂ may be connected to each other to form a cyclic group.

Description

FIELD OF THE INVENTION

[0001] 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.

BACKGROUND OF THE INVENTION

[0002] In general, the development of a silver halide photographic material is often done with an automatic developing machine for the sake of rapidity, simplicity and handleability. Further, in the development of a black-and-white photographic light-sensitive material, 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.

[0003] As 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. In the field of photographic light-sensitive materials for plate making or X-ray photographic materials, which are mostly in the form of black-and-white light-sensitive material sheet that varies in size (0.3 to 1.2 m), roller carrying type automatic developing machines are mainly used because of ease of operation, rapidity, stability, etc.

[0004] 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. In particular, 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. If the roller is in the interface of the solution with air, 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.

[0005] 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.

[0006] However, if the replenishment rate is reduced, 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. When silver stain occurs, silver 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.

[0007] Furthermore, in the photomechanical processes in the field of printing and copying, particularly plate assembly and contact work, the operation is conducted in a brighter atmosphere to improve the working efficiency and working circumstances, and silver halide photographic materials have been proposed for plate making which can be handled in circumstances that can be substantially called daylight.

[0008] Accordingly, 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.

[0009] In order to allow the photographic light-sensitive material for use in daylight contact works to process such photographic properties with a lower amount of silver, a fine particle emulsion is preferably used. In particular, a method has been known 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.

[0010] However, it is well known that 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.

[0011] Thus, 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. Thus, the developing apparatus requires regular cleaning and maintenance.

[0012] One known method for reducing silver sludging is by adding a compound capable of diminishing silver ions dissolving into the developer and/or controlling reduction of silver ions into silver as disclosed in JP-A-56-24347 (the term "JP-A" as used herein means an "unexamined published Japanese patent application"). This method, however, inevitably retards development itself and lowers sensitivity. Such a sensitivity lowering is a serious drawback for a photosensitive material/development system which is desired to have as high sensitivity as possible. Although it is quite effective for rapid processing to reduce the thickness of photosensitive material (e.g., protective layer), processing of such relatively thin photosensitive material through the processor on the running mode suffers from the problem that more silver ions are dissolved into the developer, aggravating silver sludging. The method of JP-A-56-24347 is insufficient in preventing silver sludging. There is a desire for a further improvement.

[0013] 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.

[0014] Mercaptopyrimidine compounds are known from early days and some have been utilized in the photographic art. U.S. Patent 3,240,603 and UK Patent 957,807 utilize mercaptopyrimidine compounds as fixing agents for silver halides. High pH solutions of mercaptopyrimidine compounds in high concentrations are effective fixers. In fact, at least 8 grams of mercaptopyrimidine compound is used in U.S. Patent 3,240,603.

[0015] JP-B-60-24464 utilizes mercaptopyrimidine compounds in bleach-fixing solution for promoting bleaching action.

[0016] 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.

[0017] 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.

[0018] 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.

[0019] 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.

[0020] 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.

[0021] As mentioned above, there are known a number of examples utilizing mercaptopyrimidine compounds in processing solution. Several mercaptopyrimidine compounds are used as fixers in concentrated high pH solution form while some are known as agents for preventing silver sludge. Since heretofore known mercaptopyrimidine compounds are not fully effective for preventing silver sludge, there is a need for a substantial improvement.

[0022] 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. Exemplary ate 1-morpholinopropyl-5-mercaptotetrazole and 1-morpholinoethyl-2-mercaptoimidazole. These compounds were not found to be fully effective for preventing silver sludge.

[0023] Several mercaptotriazine compounds have been used in the photographic art. 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.

[0024] 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.

SUMMARY OF THE INVENTION

[0025] It is therefore an object of the present invention first to reduce the generation of silver stain in a development tank and/or on a development rack or roller, second to facilitate the maintenance of an automatic developing machine or developing apparatus, third to reduce the generation of silver stain without having any effect on the photographic properties, and fourth to reduce the generation of silver stain without impairing the stability of the developer, when the replenishment rate of the developer is reduced upon the processing of a silver halide photographic material in an automatic developing machine with a development zone having a reduced opening value, and when a silver halide photographic material comprising finely divided grains having a high silver chloride content is developed in such a manner.

[0026] These objects of the present invention are accomplished by 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 sulfamoyl group, an arloxy group, or an alkoxy group, with the proviso that R₁ and R₂ may be connected to each other to form a cyclic group.

[0027] More remarkable effects can be obtained when 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 µm or less is processed with a developer containing the compound represented by the general formula (I).

[0028] Further, by incorporating a hydrazine derivative or tetrazolium compound in the photographic light-sensitive material, combined with the above mentioned approach, the photographic light-sensitive material can exert its effects remarkably when ultrahigh contrast is required.

DETAILED DESCRIPTION OF THE INVENTION

[0029] Examples of an alkali metal atom include Na and K, and examples of a halogen atom include F, Cl, Br and I.

[0030] 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.

[0031] 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.

[0032] In a preferred embodiment, either 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. In a further preferred embodiment, R₁ and R₂ are connected to each other to form a saturated 5- or 6-membered ring.

[0033] In a further preferred embodiment, 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, and 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. Specific examples of R₁ include a dimethylaminomethyl group, a morpholinomethyl group, an N-methylpiperadinylmethyl group, and a pyrrolidinylmethyl group. Specific examples of R₂ include a methyl group, an ethyl group, a phenyl group, and a p-methoxyphenyl group.

[0034] Specific examples of the compound represented by the general formula (I) are shown below, but the present invention should not be construed as being limited thereto:






   The synthesis of these compounds can be easily accomplished by the methods described in Comprehensive Heterocyclic Chemistry, vol. 3, pp. 40-56, pp. 106-142, and pp. 179-191, and The Journal of American Chemical Society, vol. 67, pp. 2,197-2,200 (1945), and vol. 76, pp 2441-2444.

[0035] 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.

[0036] By reducing the opening ratio of the development tank zone in the automatic developing machine to 0.05 or less, the air oxidation can be reduced and stable properties can be obtained under various processing atmospheric conditions, i.e., under temperature and humidity conditions during the winter or summer time and against the fluctuations of CO₂ gas concentration in the air (absorption of CO₂ gas reduces the pH of the developer to adversely affects the photographic properties). In the present invention, the opening ratio of the development tank zone is particularly preferably in the range of 0.04 to 0.001.

[0037] As a method for reducing the opening ratio there can be used one disclosed in JP-A-1-166040. In this method, 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.

[0038] 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.

[0039] 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.

[0040] 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. 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.

[0041] In the case of X-ray photographic materials, tabular silver halide emulsions are preferably used. In this case, 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.

[0042] 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 µm or less, more preferably 0.2 µm 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.

[0043] 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.

[0044] By using such a 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.

[0045] The tabular silver halide emulsion are disclosed in Cugnac and Chateau, "Evolution of the Morphology of Silver Bromide Crystals during Physical Ripening", Science E Industrie Photography, Vol, 33, No. 2 (1962), pp. 121-125, Duffin, Photographic Emulsion Chemistry, Focal Press, New York, 1966, pp. 66-72, A.P.H. Tribvilli and W.F. Smith, Photographic Journal, Vol. 80, p. 285 (1940). It can be prepared by referring to the methods disclosed in, for example, JP-A-58-127921, JP-A-58-113927 and JP-A-58-113928.

[0046] 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.

[0047] It is preferred to add the silver and halogen solutions in such a manner so that new crystal nuclei are not formed during the grain growing process.

[0048] 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.

[0049] The silver halide emulsion used in the present invention may be a polydispersed emulsion. A monodispersed emulsion having a narrow grain size distribution. Especially, 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.

[0050] The fluctuation coefficient is defined as follows:





   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.

[0051] 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.

[0052] 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.

[0053] 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.

[0054] Examples of such a rhodium salt 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.

[0055] The average grain size of such a silver halide emulsion is preferably 0.25 to 0.03 µm, more preferably 0.20 to 0.05 µm. 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.

[0056] 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.

[0057] 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. As an example of the 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. Further, 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.

[0058] For such a photographic material a silver halide emulsion which has not been subjected to chemical sensitization is preferably used.

[0059] 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).

[0060] The sensitivity of the various emulsion layers can be each determined by developing each of the various layers in the form of single layer.

[0061] These 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).

[0062] In the present invention, a hydrazine derivative or tetrazolium compound may be incorporated into the photographic light-sensitive material for the purpose of providing an ultrahigh contrast.

[0063] In the procedure for the formation or physical ripening of silver halide grains to be incorporated into the silver halide emulsion of the present invention, 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. In particular, for the purpose of providing a higher contrast or improving the reciprocity law failure properties, 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.

[0064] 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.

[0065] 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.

[0066] 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.

[0067] Further, a method which comprises the combined use of polyvinyl pyrrolidone and a thiosulfate as reported by Moisar and Klein Gelatione, "Proc. Symp.", 2nd, pp. 301-309, 1970, may be used with excellent results.

[0068] 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.

[0069] 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.

[0070] The silver halide grains to be used in the present invention are preferably subjected to spectral sensitization with a sensitizing dye.

[0071] 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.

[0072] In particular, 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.

[0073] 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.

[0074] 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.

[0075] 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).

[0076] Examples of such 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, alkylbenzenesulfonate, alkylnaphthalenesulfonate, alkylsulfuric ester, alkylphosphoric ester, N-acyl-N-alkyltaurine, a sulfosuccinic ester, sulfoalkyl polyoxyethylenealkylphenylether, polyoxyethylenealkylphosphoric ester), amphoteric surface active agents such as an amino acid, an aminoalkylsulfonic acid, an aminoalkylsufuric or phosphoric ester, an alkylbetaine and an amino oxide, and cationic surface active agents such as an alkylamine salt, aliphatic or aromatic quaternary ammonium salt, heterocyclic quaternary ammonium salt (e.g., pyridinium, imidazolium), and aliphatic or heterocyclic group-containing phosphonium or sulfonium salt.

[0077] 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.

[0078] The photographic light-sensitive material of the present invention may further comprise an interlayer, a filter layer, an anti-halation layer, etc. as necessary.

[0079] 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).

[0080] In order to provide an excellent adaptability to rapid processing, 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.

[0081] The binder or protective colloid to be incorporated into the hydrophilic emulsion may be gelatin. Other hydrophilic colloids may also be used. Examples of such 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.

[0082] 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.

[0083] 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. If such 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. On the other hand, as 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.

[0084] 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.

[0085] In the present invention, as 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 µm, particularly 2 to 5 µm.

[0086] In the silver halide photographic material of the present invention, 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. In a double-sided film such as direct medical X-ray film, an emulsion for the purpose of crossover cut may be provided under the emulsion layer. Examples of such a dye 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.

[0087] In the application of these dyes, it is an effective technique to mordant a specific layer in the photographic light-sensitive material with an anionic dye using a polymer having a cation site. In this case, it is preferable to use a dye which undergoes decolorization irreversibly in the development-fixing-rinse steps. 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.

[0088] As 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.

[0089] The polymer having a cation site is preferably an anion-exchanged polymer.

[0090] 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.

[0091] Examples of these 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.

[0092] These 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.

[0093] As a method for fixing the dye there can be effectively used a solid dispersion method as disclosed in JP-A-55-155350 and WO88/04794.

[0094] 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. Patents 4,080,207, 4,269,929, 4,276,364, 4,278,748, 4,385,108, 4,459,347, 4,560,638, and 4,478,928, British Patent 2,011,391B, JP-A-60-179734, JP-A-62-270948, JP-A-63-29751, JP-A-61-170733, JP-A-61-270744, and JP-A-62-948, EP 217,310, JP-A-63-32538, JP-A-63-104047, JP-A-63-121838, JP-A-63-129337, JP-A-63-234245, JP-A-63-234246, JP-A-63-223744, JP-A-63-294552, JP-A-63-306438, and JP-A-64-10233, U.S. Patent 4,686,167, JP-A-62-178246, JP-A-63-234244, JP-A-64-90439, JP-A-1-276128, JP-A-1-283548, JP-A-1-280747, JP-A-1-283549, JP-A-1-285940, JP-A-2-2541, JP-A-2-139538, JP-A-2-177057, JP-A-2-198440, JP-A-2-198441, JP-A-2-198442, JP-A-2-196234, JP-A-2-196235, JP-A-2-220042, JP-A-2-221953, and JP-A-2-221954.

[0095] 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 R₀ or R₁ each represents a hydrogen atom or one of R₀ and R₁ represents a hydrogen atom and the other represents a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group or a substituted or unsubstituted acyl group, with the proviso that B, R₁ and the hydrazine nitrogen atoms to which R and R₁ are connected may form a partial structure


of hydrazine.

[0096] In general formula (II), 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). Examples of such an alkyl group 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.

[0097] In general formula (II), 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.

[0098] 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. Typical examples of such 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).

[0099] 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.

[0100] The group represented by A may comprise a ballast group commonly used in an immobile photographic additive such as a coupler. Such 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.

[0101] 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.

[0102] 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.

[0103] 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, phenylcarbamoyl), a sulfamoyl group (e.g., dimethylsulfamoyl), an alkoxycarbonyl group (e.g., methoxycarbonyl, methoxyethoxycarbonyl), an aryloxycarbonyl group (e.g., phenoxycarbonyl), an alkoxysulfonyl group (e.g., methoxysulfonyl, ethoxysulfonyl), a thioacyl group (such as alkyl- and aryl-thioacyl group; e.g., methylthiocarbonyl), a thiocarbamoyl group (e.g., methylthiocarbamoyl), or a heterocyclic group (such as a 4- to 8-membered heterocyclic group containing at least one of N, O and S atoms as a hetero atom, e.g., pyridine ring).

[0104] Among these groups a formyl group and an acyl group are especially preferable.

[0105] 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. Examples of 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.

[0106] Most preferred among these groups represented by R₀ or R₁ is a hydrogen atom.

[0107] Specific examples of the compound represented by general formula (II) are shown below, but the present invention should not be construed as being limited thereto:


















   Methods for production of the hydrazine derivatives are disclosed in, for example, JP-A-53-20921, JP-A-53-20922, JP-A-53-66732, JP-A-53-20318, JP-A-56-67843, JP-A-62-178246, JP-A-62-180361, JP-A-63-121838, JP-A-63-234245, JP-A-63-294552, JP-A-63-306438, and U.S. Patents 4,459,347, 4,478,928, and 4,560,638.

[0108] If 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)).

[0109] When the hydrazine derivative to be used in the present invention 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.

[0110] If the hydrazine derivative to be used in the present invention is to be incorporated into the silver halide emulsion, 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. In a particularly preferred embodiment, the compound may be incorporated in a coating solution which has been prepared for coating.

[0111] 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.

[0112] 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.

[0113] Further, in this ultrahigh contrast system, a redox compound which releases a development inhibitor may be used in combination with the above mentioned compounds. Such 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.

[0114] 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.

[0115] 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. 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.

[0116] Specific examples of the tetrazolium compound to be used in the present invention are given below, but the present invention should not be construed as being limited thereto:

(1) 2-(Benzothiazole-2-il)-3-phenyl-5-dodecyl-2H-tetrazolium-bromide

(2) 2,3-Diphenyl-5-(4-t-octyloxyphenyl)-2H-tetrazolium-chloride

(3) 2,3,5-triphenyl-2H-tetrazolium

(4) 2,3,5-Tri(p-carboxyethylphenyl)-2H-tetrazolium

(5) 2-(Benzothiazole-2-il)-3-phenyl-5-(o-chlorophenyl)-2H-tetrazolium

(6) 2,3-Diphenyl-2H-tetrazolium

(7) 2,3-Diphenyl-5-methyl-2H-tetrazolium

(8) 3-(p-Hydroxyphenyl)-5-methyl-2-phenyl-2H-tetrazolium

(9) 2,3-Diphenyl-5-ethyl-2H-tetrazolium

(10) 2,3-Diphenyl-5-n-hexyl-2H-tetrazolium

(11) 5-Cyano-2,3-diphenyl-2H-tetrazolium

(12) 2-(Benzothiazole-2-il)-5-phenyl-3-(4-tolyl)-2H-tetrazolium

(13) 2-(Benzothiazole-2-il)-5-(4-chlorophenyl)-3-(4-nitrophenyl)-2H-tetrazolium

(14) 5-Ethoxycarbonyl-2,3-di(3-nitrophenyl)-2H-tetrazolium

(15) 5-Acetyl-2,3-di(p-ethoxyphenyl)-2H-tetrazolium

(16) 2,5-Diphenyl-3-(p-tolyl)-2H-tetrazolium

(17) 2,5-Diphenyl-3-(p-iodophenyl)-2H-tetrazolium

(18) 2,3-Diphenyl-5-(p-diphenyl)-2H-tetrazolium

(19) 5-(p-Bromophenyl)-2-phenyl-3-(2,4-6-trichlorophenyl)-2H-tetrazolium

(20) 3-(p-Hydroxyphenyl)-5-(p-nitrophenyl)-2-phenyl-2H-tetrazolium

(21) 5-(3,4-Dimethoxyphenyl)-3-(2-ethoxyphenyl)-2-(4-methoxyphenyl)-2H-tetrazolium

(22) 5-(4-Cyanophenyl)-2,3-diphenyl-2H-tetrazolium

(23) 3-(p-Acetamidophenyl)-2,5-diphenyl-2H-tetrazolium

(24) 5-Acetyl-2,3-diphenyl-2H-tetrazolium

(25) 5-(Fur-2-il)-2,3-diphenyl-2H-tetrazolium

(26) 5-(Thien-2-il)-2,3-diphenyl-2H-tetrazolium

(27) 2,3-diphenyl-5-(pyrido-4-il)-2H-tetrazolium

(28) 2,3-Diphenyl-5-(quinole-2-il)-2H-tetrazolium

(29) 2,3-Diphenyl-5-(benzooxazole-2-il)-2H-tetrazolium

(30) 2,3-Diphenyl-5-nitro-2H-tetrazolium

(31) 2,2',3,3'-Tetraphenyl-5,5'-(1,4-butylene)-di-(2H-tetrazolium)

(32) 2,2',3,3'-Tetraphenyl-5,5'-p-phenylene-di-(2H-tetrazolium)

(33) 2-(4,5-Dimethylthiazole-2-il)-3,5-diphenyl-2H-tetrazolium

(34) 3,5-Diphenyl-2-(triazine-2-il)-2H-tetrazolium

(35) 2-(Benzothiazole-2-il)-3-(4-methoxyphenyl)-5-phenyl-2H-tetrazolium

(36) 2,3-Dimethoxyphenyl-5-phenyl-2H-tetrazolium

(37) 2,3,5-Tris(methoxyphenyl)-2H-tetrazolium

(38) 2,3-Dimethylphenyl-5-phenyl-2H-tetrazolium

(39) 2,3-Dihydroxyethyl-5-phenyl-2H-tetrazolium

(40) 2,3-Dihydroxymethyl-5-phenyl-2H-tetrazolium

(41) 2-Cyano-3-hydroxyphenyl-5-phenyl-2H-tetrazolium

(42) 2,3-Di(p-chlorophenyl)-5-phenyl-2H-tetrazolium

(43) 2,3-Di(hydroxyethoxyphenyl)-5-phenyl-2H-tetrazolium

(44) 2,3-Di(2-pyridyl)-5-phenyl-2H-tetrazolium

(45) 2,3,5-tris(2-pyridyl)-2H-tetrazolium

(46) 2,3,5-Tris(4-pyridyl)-2H-tetrazolium

   If the tetrazolium compound to be used is a nondiffusive compound, a nondiffusive compound obtained by reacting a nondiffusive compound among the above mentioned exemplary compounds with an anion may be used.

[0117] 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.

[0118] By properly selecting an anion moiety and a cation moiety, 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. In order to make a uniform dispersion, an ultrasonic wave or a suitable homogenizer such as MANTONGORIN (trade name) homogenizer may be used to make the emulsion dispersion.

[0119] As mentioned above, 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.

[0120] Tetrazolium compounds may be used singly or in combination.

[0121] 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.

[0122] 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. In particular, there can be used many compounds known as fog inhibitors or stabilizers. Examples of 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, benzenethiosulfonic acid, benzenesulfinic acid, and benzenesulfonic amide. Preferred among these compounds are benzotriazoles (e.g., 5-methyl-benzotriazole) and nitroindazoles (e.g., 5-nitroindazole). These compounds may be incorporated into the processing solution. 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.

[0123] 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.

[0124] The photographic light-sensitive material may contain an inorganic or organic film hardener in the photographic emulsion layer or other hydrophilic colloidal layers. For example, chromium salts (e.g., chromium alum, chromium acetate), aldehydes (e.g., formaldehyde, glutaraldehyde), N-methylol compounds (e.g., dimethylolurea), dioxane derivatives, 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.

[0125] 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.

[0126] Specific examples of such a hydroquinone derivative 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.

[0127] 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. For example, 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.

[0128] 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. Examples of such 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. 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. Particularly preferred among these compounds are 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.

[0129] 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.

[0130] Various photographic additives which can be used in the present invention are described in, e.g., the above cited Research Disclosure Nos. 17643, pp. 23-28, and ibid., 18716, pp. 648-651. The type of an additive and the position where they are described in detail is given below.

	Kind of additive	RD17643	RD18716
1.	Chemical Sensitizer	p. 23	p. 648, Right Column
2.	Sensitivity Increasing Agent		do.
3.	Spectral Sensitizer, Supersensitizer	pp. 23-24	p. 648, Right Column-p. 649, Right Column
4.	Brigthening Agent		p. 24
5.	Fog Inhibitor, Stabilizer	pp. 24-25	p. 649, Right Column
6.	Light Absorbent, Filter Dye, Ultraviolet Absorbent	pp. 25-26	p. 649, Right Column-p. 650 Left Column
7.	Stain Inhibitor	p. 25, Right Column	p. 650, Left to Right Column
8.	Dye Image Stabilizer	p. 25
9.	Film Hardener	p. 26	p. 651, Left Column
10.	Binder	p. 26	do.

[0131] 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.

[0132] 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.

[0133] 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.

[0134] Examples of p-aminophenol developing agents to be used in the present invention include N-methyl-p-aminophenol, p-aminophenol, N-(β-hydroxyethyl)-p-aminophenol, and N-(4-hydroxyphenyl)glycine. Particularly preferred among these p-aminophenol developing agents is N-methyl-p-aminophenol.

[0135] 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.

[0136] 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. Such 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.

[0137] As an alkali agent to be used in the adjustment of the pH value there can be used an ordinary water-soluble inorganic alkaline metal salt (e.g., sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate).

[0138] Examples of 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. Further, a toner, a surface active agent, an anti-foaming agent, a water softener, a film hardener, etc., may be contained in the developer.

[0139] 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.

[0140] 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.

[0141] 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.

[0142] For the purpose of saving carrying cost, packaging cost or space, the processing solution is preferably concentrated so that it is diluted before use. For the concentration of the developer, it is effective to use a potassium salt as a salt component to be contained in the developer.

[0143] As 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.

[0144] 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.

[0145] 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.

[0146] 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.

[0147] 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.

[0148] In order to accelerate the elution of dyes, a compound as disclosed in JP-A-64-4739 may be used.

[0149] 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.

[0150] The effects of the present invention can be exerted regardless of the presence of a film hardener.

[0151] 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.

[0152] The replenishment rate of the fixing solution is preferably in the range of 600 ml/m² or less, particularly 450 ml/m² or less.

[0153] The photographic light-sensitive material which has been developed and fixed is then rinsed or stabilized.

[0154] 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. In other words, the system of the present invention not only enables water-saving processing, but also requires no piping in the automatic developing machine.

[0155] If the rinse is conducted with a small amount of water, 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.

[0156] Further, 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.

[0157] In order to inhibit unevenness due to bubbling which is easily caused when the rinse is effected with a small amount of water and/or to inhibit the transfer of the processing components attached to the squeeze roller to the processed film, a water-soluble surface active agent or anti-foaming agent may be added.

[0158] In order to inhibit stain from a dye eluted from the photographic light-sensitive material, a dye adsorbent as described in JP-A-63-163456 may be provided in the washing tank.

[0159] Further, the rinse may be followed by stabilizing. By way of example, 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.

[0160] 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.

[0161] In the development procedure of the present invention, 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.

[0162] 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.

[0163] The washing and stabilizing temperatures are preferably in the range of 0 to 50°C.

[0164] In accordance with the process of the present invention, 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.

[0165] The present invention will be further described in the following examples, but the present invention should not be construed as being limited thereto.

EXAMPLE 1

[1] Preparation of emulsions

[0166] 

Preparation of 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

[0167] 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 µm. Subsequently, 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

[0168] The material was then rinsed in accordance with an ordinary flocculation method. 30 g of gelatin was then added to the material.

[0169] 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.

[0170] 200 mg of 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene as a stabilizer and phenoxyethanol as a preservative were added to the material. Eventually, an emulsion of cubic silver bromochloroiodide grains having a silver chloride content of 70 mol% and an average grain diameter of 0.2 µm was obtained. (Fluctuation coefficient: 9%)

Preparation of coat specimen

[0171] 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. Further, 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. On the coat layer were simultaneously coated 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 µm	50 mg/m²
Compound 1 (gelatin dispersion)	30 mg/m²
Colloidal silica having a grain diameter of 10 to 20 mµm	30 mg/m²
Compound 2	5 mg/m²
Sodium dodecylbenzenesulfonate	22 mg/m²

Compound 1

[0172] 

Compound 2

[0173] 


   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

Compound 3

[0174] 

Compound 4

[0175] 

Compound 5

[0176] 

[0177] 

[Back protective layer]
Gelatin	0.5 g/m²
Polymethyl methacrylate (grain size: 4.7 µm)	30 mg/m²
Sodium dodecylbenzenesulfonate	20 mg/m²
Compound 2	2 mg/m²
Compound 1 (gelatin dispersion)	100 mg/m²

[0178] The coat specimen thus prepared hereinafter referred to as "Film A". 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.

[0179] 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

[0180] Based on the developer thus prepared, testing developers as set forth in Table 1 were prepared.

TABLE 1

Developer No.	Compound of general formula (I)
	Compound No.	Added amount
1 (comparative example)	--	--
2 (present invention)	I-4	0.09 g/ℓ
3 (present invention)	I-6	0.15 g/ℓ
4 (present invention)	I-7	0.16 g/ℓ
5 (present invention)	I-11	0.10 g/ℓ

[0181] As 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

[0182] 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.

[0183] These specimens were then subjected to a running test by means of an automatic developing machine FG-680A (opening ratio: 0.065) available from Fuji Photo Film Co., Ltd. and an automatic developing machine whose development tank had been adjusted by a floating cover and an intermittent operation (1-minute operation-9-minute suspension cycle is repeated when no films are passed) to an opening ratio of 0.030. Each automatic developing machine had been remodelled to enable 38°C-11" processing (development).

[0184] The term "opening ratio" as used herein means an opening ratio in operation (dynamic opening ratio) or opening ratio during suspension (static opening ratio) averaged over the respective allocated time.

[0185] In the running test, 40 sheets of each film of full-size (50.8 cm × 60.1 cm) which had been half-exposed were processed for 6 consecutive days, and the operation was suspended for one day. This running test was conducted three times. The replenishment rate was and 100 ml or 50 ml for developer and 50 ml for fixing solution per sheet of full-size specimen. The composition of the replenishing solution was the same as the developer shown hereinabove.

[0186] Evaluation of the photographic properties was conducted as follows. Gradation was determined by dividing the difference between a density of 3.0 and a density of 0.1 by the difference between the logarithm of the exposure giving a density of 3.0 and the logarithm of the exposure giving a density of 0.1. Sensitivity was represented relative to the reciprocal of the exposure required to give a density of 1.5 when the photographic light-sensitive material is processed with a fresh batch of Developer No. 1 as 100.

[0187] Silver stain was visually evaluated by five conditions.

[0188] 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.

[0189] Table 2 shows the results of the photographic properties and silver stain in the running test.

[0190] Table 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.

[0191] Thus, 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.

[0192] 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.

EXAMPLE 2

(1st light-sensitive emulsion layer)

Preparation of light-sensitive emulsion A

[0193] To 700 ml of a 2% aqueous solution of gelatin containing sodium chloride (0.06 M) and 1,3-dimethyl-2-imidazolidinethione (1.3×10⁻⁴ M) were added an aqueous solution containing 0.37M silver nitrate and an aqueous solution of halogen salt containing (NH₄)₃RhCl₆ in an amount of 1×10⁻⁷ mol per mol of silver, K₃IrCl₆ in an amount of 5×10⁻⁷ mol per mol of silver, 0.11 M potassium bromide and 0.27 M sodium chloride at a temperature of 45°C over 12 minutes with stirring by the double jet process to obtain silver bromochloride grains with an average grain size of 0.20 µm and a silver chloride content of 70 mol% so as to form nuclei. To the material were added simultaneously an aqueous solution containing 0.63 M silver nitrate and an aqueous solution of halogen salt containing 0.19 M potassium bromide and 0.47 M sodium chloride over 20 minutes by the double jet process. To the material was added 1×10⁻³ mol of KI solution to make conversion. The material was then rinsed by an ordinary flocculation method. 40 g of gelatin (per 80 g of silver) was added into the material and the mixture was then adjusted to a pH value of 6.5 and a pAg value of 7.5. 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. As 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. Thus, cubic silver bromochloride grains having an average grain size of 0.28 µm and a silver chloride content of 70 mol% were obtained. (Fluctuation coefficient: 9%)

Coating of 1st light-sensitive emulsion layer

[0194] To the emulsion batch were then added potassium salt of 5-[3-(4-sulfobutyl)-5-chloro-2-benzooxazolidilidene]-1-hydroxyethoxyethyl-3-(2-pyridyl)-2-thiohydantoin, 1-phenyl-5-mercaptotetrazole, and Compound (a) as shortwave cyanine dye represented by the following structural formula in an amount of 1×10⁻³ mol, 2×10⁻⁴ mol and 5×10⁻⁴ mol per mol of silver, respectively, and 200 mg/m² of Compound (b) as a polymer, 50 mg/m² of hydroquinone, 200 mg/m² of a polyethyl acrylate dispersion, 200 mg/m² of 1,3-bisvinylsulfonyl-2-propanol as a film hardener, and a hydrazine compound (c) having the following chemical structure.

Compound (a)

[0195] 

Compound (b)

[0196] 

Hydrazine compound (c)

[0197] 

(Coating of interlayer)

[0198] 

Gelatin	1.0 g/m²
1,3-Bisvinylsulfonyl-2-propanol	4.0 wt% based on gelatin

(2nd light-sensitive emulsion layer)

Preparation of light-sensitive emulsion B

[0199] To 700 ml of a 2% aqueous solution of gelatin containing sodium chloride (0.0.6M) and 1,3-dimethyl-2-imidazolidinethione (1.3×10⁻⁴ M) were added an aqueous solution contianing 1.0 M silver nitrate and an aqueous solution of halogen salt containing (NH₄)₃RhCl₆ in an amount of 3×10⁻⁷ mol per mol of silver, 0.3 M potassium bromide and 0.74 M sodium chloride at a temperature of 45°C over 30 minutes with stirring by the double jet process to obtain silver bromochloride grains with an average grain size of 0.28 µm and a silver chloride content of 70 mol%. The material was then rinsed by an ordinary flocculation method. 40 g (per 80 g of silver) of gelatin was added into the material and the mixture was then adjusted of gelatin to a pH value of 6.5 and a pAg value of 7.5. The emulsion was then subjected to chemical sensitization with sodium thiosulfate and chloroauric acid in an amount of 5 mg and 8 mg, respectively, and the emulsion was heated at a temperature of 60°C for 60 minutes. As stabilizers there was added 150 mg (per mol of Ag) of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene. Thus, cubic silver bromochloride grains having an average grain size of 0.28 µm and a silver chloride content of 70 mol% were obtained. (Fluctuation coefficient: 10%)

Coating of 2nd light-sensitive emulsion layer

[0200] 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 g/m² and 0.3 g/m², respectively.

(Coating of protective layer)

[0201] As a protective layer, 1.0 g/m² of gelatin and 0.3 g/m² of polymethyl methacrylate grains (average grain diameter: 2.5 µm) were coated on the material using the following surface active agents:

Surface active agent

[0202] 


   The back layer and back protective layer were coated with the following formulations:

[Formulations of Back layer]

[0203] 

Gelatin	3 g/m²
Latex: polyethyl acrylate	2 g/m²
Surface active agent: Sodium p-dodecylbenzenesulfonate	40 mg/m²

Gelatin hardener

[0204] 

Dye: mixture of Dyes [a], [b] and [c]

[0205] 

Dye [a]	50 mg/m²
Dye [b]	100 mg/m²
Dye [c]	50 mg/m²

Dye (a)

[0206] 

Dye (b)

[0207] 

Dye (c)

[0208] 

[Back protective layer]

[0209] 

[0210] Onto a polyester film (100 µm) 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.

[0211] The composition of the developer is given below.

[0212] The composition of the replenisher for the developer has the same composition as this developer.

Developer
Hydroquinone	50.0 g
N-methyl-p-aminophenol	0.3 g
Sodium hydroxide	18.0 g
5-Sulfosalicylic acid	30.0 g
Boric acid	25.0 g
Potassium sulfite	124.0 g
Disodium ethylenediaminetetraacetate	1.0 g
Potassium bromide	10.0 g
5-Methylbenzotriazole	0.4 g
Sodium 3-(5-mercaptotetrazole) benzenesulfonate	0.2 g
N-n-butyldiethanolamine	15.0 g
Sodium toluenesulfonate	8.0 g
Sodium 2-mercaptobenzimidazole-5-sulfonate	0.3 g
Water to make	1 ℓ
pH (adjusted with potassium hydroxide)	11.6

[0213] Based on the developer thus prepared, testing developers as set forth in Table 3 were prepared.

TABLE 3

Developer No.	Compound of general formula (I)
	Compound No.	Added amount
1 (comparative example)	--	--
2 (present invention)	I-3	0.09 g/ℓ
3 (present invention)	I-4	0.09 g/ℓ
4 (present invention)	I-9	0.12 g/ℓ
5 (present invention)	I-11	0.10 g/ℓ

[0214] 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.

[0215] 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.

[0216] The running test of these light-sensitive materials with these developers gave results similar to those of Example 1 as shown in Table 4. It was thus found that even in processing with a reduced opening ratio at a reduced replenishment rate, the use of a compound of the present invention provides a high effect of inhibiting silver stain without affecting the photographic properties.

EXAMPLE 3

(1) Preparation of emulsion [Emulsion D]

[0217] To an aqueous solution of gelatin which had been kept at a temperature of 35°C were added simultaneously an aqueous solution of silver nitrate and an aqueous solution of sodium chloride containing (NH₄)₂Rh(H₂O)Cl₅ in an amount of 4×10⁻⁵ mol per mol of silver over 3.5 minutes with the potential thereof being controlled to 95 mV to prepare core grains having a diameter of 0.11 µm. To the material were added simultaneously an aqueous solution of silver nitrate and an aqueous solution of sodium chloride containing (NH₄)₂Rh(H₂O)Cl₅ in an amount of 1.2×10⁻⁴ mol per mol of silver over 7 minutes with the potential thereof being controlled to 95 mV. After this addition, 5,6-cyclopentane-4-hydroxy-1,3,3a,7-tetrazaindene (5×10⁻³ mol per mol of silver) was added to the system to stop physical ripening. Thus, cubic silver chloride grains having an average grain size of 0.14 µm were prepared.

[Emulsion E]

[0218] 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 µm.

Preparation of coat specimens

[0219] To each of these emulsions were added 24 mg/m² of 5,6-cyclopentane-4-hydroxy-1,3,3a,7-tetrazaindene, 770 mg/m² of an ethyl acrylate latex (average grain diameter: 0.05 µm), 3 mg/m² of a compound having the following chemical structure, and 126 mg/m² of 2-bis-(vinylsulfonylacetamide) ethane as a film hardener. These emulsions were each coated on a polyester support in an amount of 3.0 g/m² as calculated in terms of silver. Coated gelatin amount was 1.5 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 µm) as a protective lower layer. On the lower layer were coated 0.7 g/m² of gelatin and a dye having the following chemical structure in the form of a solid dispersion as an upper protective layer. At the same time, 55 mg/m² of a matting agent (silicon dioxide; average grain diameter: 3.5 µm), 135 mg/m² of methanol silica (average grain diameter: 0.02 µm), 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%.)

(Back layer)

[0220] 

Gelatin	170 mg/m²
Sodium dodecylbenzenesulfonate	32 mg/m²
Dihexyl succinate-α-sulfonic acid sodium salt	35 mg/m²
SnO₂/Sb (a 9/1 mixture (weight ratio); average grain diameter: 0.25 µm)	318 mg/m²

(Back protective layer)

[0221] 

[0222] 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".

[0223] 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

[0224] By adding the compound represented by formula (I) shown in Table 5 into the developer thus prepared, Developer Nos. 1 to 5 for tests were prepared.

TABLE 5

Developer No.	Compound of general formula (I)
	Compound No.	Added amount
1 (comparative example)	--	--
2 (present invention)	I-4	0.09 g/ℓ
3 (present invention)	I-6	0.15 g/ℓ
4 (present invention)	I-7	0.16 g/ℓ
5 (present invention)	I-11	0.10 g/ℓ

[0225] As 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

[0226] 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.

[0227] These specimens were then subjected to running test in the same manner as Example 1 using an automatic developing machine FG-680A available from Fuji Photo Film Co., Ltd.) having an opening ratio of 0.030.

[0228] In the running test, 40 sheets of each film of full-size (50.8 cm × 60.1 cm) which had been half-exposed were processed for 6 consecutive days, and then the operation was suspended for one day. This running test was conducted three times.

[0229] 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.

[0230] Evaluation of the photographic properties was conducted as follows. Gradation was determined by dividing the difference between a density of 3.0 and a density of 0.1 by the difference between the logarithm of the exposure giving a density of 3.0 and the logarithm of the exposure giving a density of 0.1. Sensitivity was represented relative to the reciprocal of the exposure required to give a density of 1.5 when the photographic light-sensitive material is processed with a fresh batch of Developer No. 1 as 100. Dmax was represented by the maximum blackening density developed when an exposure is given such that 50% dot area in a dot image on the original can be contact worked to 50% dot area.

[0231] Silver stain was visually evaluated by five conditions as in Example 1.

[0232] Table 6 shows the results of the photographic properties and silver stain in the running test.

[0233] 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.

[0234] It can thus be seen that even a silver chloride photographic material comprising reduced size grains can show little silver stain with no change in photographic properties when processed with a developer containing a compound of the present invention.

EXAMPLE 4

(1) Preparation of emulsion [Emulsion F]

[0235] To an aqueous solution of gelatin which had been kept at a temperature of 35°C were added simultaneously an aqueous solution of silver nitrate and an aqueous solution of sodium chloride containing (NH₄)₂Rh(H₂O)Cl₅ in an amount of 4×10⁻⁵ mol per mol of silver over 3.5 minutes with the potential thereof being controlled to 95 mV to prepare core grains having a diameter of 0.11 µm. To the material were added simultaneously an aqueous solution of silver nitrate and an aqueous solution of sodium chloride containing (NH₄)₂Rh(H₂O)Cl₅ in an amount of 1.2×10⁻⁴ mol per mol of silver over 7 minutes with the potential thereof being controlled to 95 mV. After this addition, 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene (5×10⁻³ mol per mol of silver) was added to the system to stop physical ripening. Thus, cubic silver chloride grains having an average grain size of 0.16 µm were prepared.

[Emulsion G]

[0236] 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 µm.

Preparation of coat specimens

[0237] To each of 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 µm), 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 µm) 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. At the same time, 55 mg/m² of a matting agent (silicon dioxide; average grain diameter: 3.5 µm), 135 mg/m² of methanol silica (average grain diameter: 0.02 µm), 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%.)

(Back layer)

[0238] 

Gelatin	170 mg/m²
Sodium dodecylbenzenesulfonate	32 mg/m²
Dihexyl succinate-α-sulfonic acid sodium salt	35 mg/m²
SnO₂/Sb (9/1 (weight ratio); (average grain diameter: 0.25 µm)	318 mg/m²

(Back protective layer)

[0239] 

[0240] The composition of the developer is given below.

Developer
Hydroquinone	50.0 g
N-methyl-p-aminophenol	0.3 g
Sodium hydroxide	18.0 g
5-Sulfosalicylic acid	30.0 g
Boric acid	25.0 g
Potassium sulfite	124.0 g
Disodium ethylenediaminetetraacetate	1.0 g
Potassium bromide	10.0 g
5-Methylbenzotriazole	0.4 g
Sodium 3-(5-mercaptotetrazole) benzenesulfonate	0.2 g
N-n-butyldiethanolamine	15.0 g
Sodium toluenesulfonate	8.0 g
Sodium 2-mercaptobenzimidazole-5-sulfonate	0.3 g
Water to make	1 ℓ
pH (adjusted with potassium hydroxide)	11.6

[0241] By adding the compound represented by formula (I) shown in Table 7 into the developer thus prepared, Developer Nos. 1 to 5 for tests were prepared.

TABLE 7

Developer No.	Compound of general formula (I)
	Compound No.	Added amount
1 (comparative example)	--	--
2 (present invention)	I-3	0.09 g/ℓ
3 (present invention)	I-4	0.09 g/ℓ
4 (present invention)	I-9	0.12 g/ℓ
5 (present invention)	I-11	0.10 g/ℓ

[0242] 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. The results are set forth in 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.

[0243] 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.

[0244] In accordance with 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.

[0245] While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.

Claims

1. 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 said silver halide photographic material which has been exposed with a developer containing a compound represented by 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, as 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 sulfamoyl group, an aryloxy group, or an alkoxy group, with the proviso that R₁ and R₂ may be connected to each other to form a cyclic group.

2. The method for processing a silver halide photographic material as in claim 1, wherein said opening ratio is 0.04 to 0.001.

3. The method for processing a silver halide photographic material as in claim 1, wherein said cyclic group formed by R₁ and R₂ is a 5- to 6-membered hydrocarbon ring or a 5- or 6-membered heterocyclic group having at least one of N, O and S atoms as a hetero atom.

4. The method for processing a silver halide photographic material as in claim 1, wherein said alkyl group, aryl group, aralkyl group, amino group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, sulfamoyl group and alkoxy group are substituted groups with at least one substituent selected from the group consisting of an alkyl group, an aryl group, an aralkyl group, a hydroxyl group, -SM, -COOM, -SO₃M, -PO(OM)₂ (wherein M represents a hydrogen atom, as 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 sulfamoyl group, an aryloxy group, an alkoxy group, and a heterocyclic group, and said substituted groups may be further substituted with at least one of said substituents.

5. The method for processing a silver halide photographic material as in claim 4, wherein said heterocyclic group is a 5- or 6-membered heterocyclic group having at least one of N, O and S atoms as a hetero atom.

6. The method for processing a silver halide photographic material as in claim 1, wherein the sum of the carbon atoms contained in R₁ and R₂ is 2 to 20.

7. The method for processing a silver halide photographic material as in claim 1, wherein said compound is incorporated in an amount of 0.01 to 100 mmol per ℓ of the developer.

8. The method for processing a silver halide photographic material as in claim 1, wherein said compound is incorporated in an amount of 0.1 to 10 mmol per ℓ of the developer.

9. The method for processing a silver halide photographic material as in claim 1, wherein said light-sensitive silver halide emulsion layer comprises silver halide grains containing at least 90 mol% of silver chloride and having an average grain diameter of 0.25 µm or less.

10. The method for processing a silver halide photographic material as in claim 9, wherein said average grain diameter is 0.25 to 0.03 µm.

11. The method for processing a silver halide photographic material as in claim 1, wherein said silver halide photographic material contains at least one compound selected from the group consisting of hydrazine derivatives and tetrazolium compounds for providing a high contrast.

12. The method for processing a silver halide photographic material as in claim 11, wherein said hydrazine derivatives are compounds represented by general formula (II):

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 or heterocyclic group; and each of R₀ or R₁ each represents a hydrogen atom or one of R₀ and R₁ represents a hydrogen atom and the other represents a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group or a substituted or unsubstituted acyl group, with the proviso that B, R₁ and the hydrazine nitrogen atoms to which R and R₁ are connected may form a partial structure

of hydrazine.

13. The method for processing a silver halide photographic material as in claim 12, wherein said hydrazine compound is incorporated into at least one of light-sensitive silver halide emulsion layer in an amount of 5×10⁻⁷ to 5×10⁻² mol per mol of silver halide in the same silver halide emulsion layer.

14. The method for processing a silver halide photographic material as in claim 12, wherein said hydrophilic colloidal layer is a light-sensitive layer and contains said hydrazine compound in an amount of 1×10⁻⁵ to 5×10⁻² mol per mol of silver halide.

15. The method for processing a silver halide photographic material as in claim 1, wherein the pH of the developer is 9 to 13.

16. The method for processing a silver halide photographic material as in claim 1, wherein the temperature of the developer is 25 to 50°C.

17. The method for processing a silver halide photographic material as in claim 1, wherein the developer is replenished in a rate of 1000 ml per m² or less of the photographic material.

18. The method for processing a silver halide photographic material as in claim 1, wherein the developer is replenished in a rate of 60 to 650 ml per m² of the photographic material.

19. The method for processing a silver halide photographic material as in claim 1, wherein said developer contains at least one of a sulfite, a thioether, a thiosulfate and an imidazole as a preservative.

20. The method for processing a silver halide photographic material as in claim 19, wherein said sulfite is incorporated in an amount of 0.20 mol per ℓ or more of the developer.