Process for developing black-and-white silver halide photographic light sensitive materials

Abstract: A method of developing an exposed black and white silver halide photographic light-sensitive material with developer using an automatic processor is disclosed, the developing comprising supplying replenisher for developer in an amount of not more than 200 ml per m² of the material, the material containing a hydrazine derivative, and the developer having a pH value of 10.0 to 11.2 and containing a dihydroxy benzene compound, a 3-pyrazolidone compound or an aminophenol compound, a sulfite of 0.3 to 1.2 mol/litre and at least one of compounds represented by the following formulae (1) and (2): Formula (1) Z-SM

Description: This invention relates to a process for developing a black-and-white silver halide photographic light-sensitive material comprising a support bearing silver halide light-sensitive layers and, particularly to a process for developing a black-and-white silver halide photographic light-sensitive material, in which a high contrast can be provided without spoiling sensitivity, and any black-spot and silver sludge production can be prevented. Photolithographic processing includes a step for converting a continuous tone original into a halftone dot image. In the step, an infectious development technique has been used as a photographic technique capable of reproducing ultra-hard contrast images. The lithographic type silver halide photographic light-sensitive materials applicable to the infectious development are comprised of, for example, a silver chlorobromide emulsion of which the grains have an average grain size of 0.2 µm, a narrow grain distribution, a uniform configuration and a high silver chloride content (at least not less than 50 mol%). When the above-mentioned lithographic type silver halide photographic light-sensitive material is processed with an alkaline hydroquinone developer having a low sulfite ion concentration, that is a so-called lithographic type developer, an image having a high contrast, high sharpness and high resolving power can be provided. However, the lithographic type developer has a very low preservability, because it is liable to be affected by air oxidation. Therefore, a constant development quality can only be maintained with difficulty when the developer is used continuously. There have been well-known processes for providing a high contrast image rapidly without making use of the above-mentioned lithographic type developer. As is found in Japanese Patent Publication Open to Public Inspection (hereinafter referred to as JP OPI Publication) No. 56-106244/1981, for example, a hydrazine derivative is contained in a silver halide photographic light-sensitive material and the light-sensitive material is processed with an alkali developer containing an amino compound. According to these processes, an image having an excellent preservability and a high contrast can be provided even when the light-sensitive material is processed with a rapid processing developer. In the above-mentioned techniques, the light-sensitive material has been processed inevitably with a developer having a pH exceeding 11.2, so that the contrast hardening property of the hydrazine derivative can satisfactorily be displayed. The developing agent of the above-mentioned developer having a pH exceeding 11.2 is liable to be oxidized when the developer is exposed to the air. When the developing agent is exposed to the air, there may be some instances where an ultra-hard contrast image may not be available, though the above-mentioned developer is relatively more stable than the lithographic type developers. For remedying the above-mentioned defects, JP OPI Publication No. 63-29751/1988 and European Patent Nos. 333,435 and 345,025 disclose silver halide photographic light-sensitive materials each containing a contrast hardener capable of hardening the contrast of the light-sensitive materials, even when a relatively low pH developer is used. According to the above-mentioned processes, the stability against air oxidation of the developers can be improved remarkably as compared to the cases of the lithographic type developers. However, for further increasing the stability, it is required to add a sulfite in an amount of not less than 0.3 mols per liter of the developer to be used. On the other hand, generally, lithographic black-and-white silver halide photographic light-sensitive materials are exposed to light and then processed through an automatic processor. In this case, it is also usual that they are so processed as to obtain stable photographic characteristics by replenishing a developer in a specific amount in proportion to the area of the light-sensitive material to be processed. For obtaining such a hard contrast image as mentioned above, the processes have been carried out so far, replenishing the developer replenisher in an amount of not less than 300 ml per liter of the developer used, so that fatigue of the processing solutions produced in a continuous processing operation and deterioration of developer produced by air oxidation can be prevented. However, with the recent increase in concern for environmental protection, it is urgently required to reduce the amount of waste developer. When hard contrast light-sensitive materials such as those mentioned above are continuously processed under conditions such that a developer is replenished in a small amount of not more than 200 ml per m 2 of the light-sensitive material, the sulfite concentration of the developer increases as mentioned above and when an automatic processor is used, a silver stain (so-called silver sludge) is liable to be produced. In the silver stain, silver is dissolved out of a light-sensitive material into a developer and a black or silver extraneous deposit adheres to various parts of an automatic processor, such as the rollers and gears thereof, resulting in contamination or damage of the surface of the light-sensitive material, spoiling the finished characteristics of the light-sensitive material. For development processes of hard contrast light-sensitive materials for lithographic printing use, it is, therefore, essential to eliminate the above-mentioned silver sludge. When a development process is carried out by making use of an automatic processor, it usually takes not less than 90 seconds from the time when inserting the leading edge of a film into the automatic processor to the point when the leading edge of the film leaves the drying zone, (the so-called Dry to Dry time). In recent years, however, it has been demanded to shorten development processing time due to the increase in the numbers of printing matters and the saving of working hours. Therefore, when a hard contrast light-sensitive material containing a hydrazine derivative is rapidly processed with the whole processing time (dry to dry) within 60 seconds with an automatic processor under conditions such as those mentioned above, it has been found that silver contamination is liable to be worse and, at the same time, the development process is liable to be unstable. A sand-shaped fog, that is, so-called black spot, peculiarly produced in a hydrazine derivative-containing light-sensitive material is liable to be produced in unexposed portions after completing the development process. Well-known silver sludge preventives against silver contamination, which may generally be added to developers include, for example, a 2-mercapto-1,3,4-thiadiazole (such as those given in British Patent No. 940,169), a 2-mercapto-1,3,4-thiadiazole or a 1-phenyl-5-mercapto-tetrazole (such as those given in US Patent No. 3,173,789), and 2-mercaptobenzoxazole and 2-mercaptobenzimidazole (each given in Photogr. Sci. Eng., 20 , p.220, 1976). However, when a processing is carried out with an alkali developer containing a hydrazine derivative and an amino compound and also with such a silver sludge preventive as mentioned above, it has been found that not only is the silver sludge preventing effect unsatisfactory, but sensitivity is lowered, contrast is softened and the black spot prevention effect is poor. It is an object of the invention to provide a process for developing a black-and-white silver halide photographic light-sensitive material, in which ultrahard contrast photographic characteristics can be obtained without spoiling any sensitivity and, at the same time preventing any silver sludge and black spot production. The above-mentioned object of the invention can be achieved in a process for developing with developer a black-and-white silver halide photographic light-sensitive material comprising a support and provided thereon, a silver halide photographic emulsion layer and/or a hydrophilic colloid layer other than the silver halide photographic emulsion layer using an automatic processor, replenisher for developer being supplied to the developer in an amount of not more than 200 ml per m 2 of the material, at least one layer of the emulsion layer and the hydrophilic colloid layer comprising a hydrazine derivative and a nucleation accelerating compound, and the developer having a pH value of from 10.0 to 11.2 and comprising the following compounds (1) to (4) : (1) a dihydroxybenzene type developing agent, (2) a 3-pyrazolidone type or aminophenol type developing agent, (3) 0.3 to 1.2 mol/litre of a sulfite, and (4) at least one compound represented by the following Formulae (1) and (2): Formula (1) Z-SM wherein Z represents an alkyl, aryl or heterocyclic group having a group selected from a hydroxy group, a -SO 3 M 1 group, a -COOM 1 group, a substituted or unsubstituted amino group and a substituted or unsubstituted ammonio group (wherein M 1 represents a hydrogen atom, an alkali metal atom or a substituted or unsubstituted ammonium ion) or a substituent having the group; and M represents a hydrogen atom, an alkali metal atom or a substituted or unsubstituted amidino group which may form a hydrogen halogenide or sulfonate salt, wherein A 1 and A 2 independently represent an aliphatic group, an alicyclic group, an aralkyl group, an aryl group, or a 5 or 6-membered heterocyclic group having hydrogen atom or a substituent; m 1 and m 2 each represent 1, 2 or 3; n represents 1 or 2; and B 1 and B 2 independently represent -COOM', -SO 3 M', -CON(X) (Y), -S-Z' or -SO 2 N(X)(Y) wherein X and Y independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group, either of which may have a hydroxy group, a carboxylic acid group or a sulfonic acid group; M' represents a monovalent cation; and Z' is synonymous with X and Y, provided that Z' is not a hydrogen atom. It is also preferred that the total processing time is within the range of from 20 to 60 seconds, when making use of an automatic processor. Now, the invention will be detailed below. The dihydroxybenzene type developing agents applicable to the developer of the invention include, for example, hydroquinone, chlorohydroquinone and methyl hydroquinone. Among them, hydroquinone is preferably used. Examples of the 3-pyrazolidone type developing agents include 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1-p-aminophenyl-4,4-dimethyl-3-pyrazolidone, 1-p-tolyl-4,4-dimethyl-3-pyrazolidone, and 1-p-tolyl-4-methyl-4-hydroxymethyl-3-pyrazolidone. Suitable aminophenol type developing agents include, preferably, N-methyl-p-aminophenol, p-aminophenol, N-(β-hydroxyethyl)-p-aminophenol, N-(4-hydroxyphenyl) glycine, 2-methyl-p-aminophenol, p-benzylaminophenol. Among them, N-methyl-p-aminophenol is preferably used. It is preferred that dihydroxybenzene type developing agents are ordinarily used in an amount within the range of from 0.05 mols/liter to 2 mols/liter. A 3-pyrazolidone or an aminophenol is preferably used in an amount of from 0.0001 to 1 mol/liter. A dihydroxybenzene is more preferably used in an amount within the range of from 0.05 to 1.5 mols/liter. A 3-pyrazolidone or an aminophenol is more preferably used in an amount of from 0.0001 to 0.2 mols/liter. The sulfite preservatives applicable to the invention include, for example, sodium sulfite, potassium sulfite, lithium sulfite, sodium bisulfite, potassium metabisulfite, and sodium formaldehyde bisulfite. The sulfites are ordinarily used in an amount of not less than 0.3 mols/liter. If too much is added, they precipitate in a developer so that the developer is contaminated. It is, therefore, advisable to use them in an amount of 1.2 mols/liter as the upper limit. In the invention, the pH value of the developer are to be within the range of 10.0 to 11.2. If the pH is lower than 10, no hard contrast image can be obtained. If the pH exceeds 11.2, fogginess is liable to increase. The pH value is preferably 10.0 to 10.9, and more preferably 10.0 to 10.7. Now, the compounds represented by Formula (1) will be detailed below. In the Formula, Z represents an alkyl, aryl or heterocyclic group having a group selected from a hydroxy group, a -SO 3 M 1 group, a -COOM 1 group, a substituted or unsubstituted amino group and a substituted or unsubstituted ammonio group (wherein M 1 represents a hydrogen atom, an alkali metal atom or a substituted or unsubstituted ammonium ion) or a substituent having the group; and M represents a hydrogen atom, an alkali metal atom or a substituted or unsubstituted amidino group which may form a hydrogen halogenide or sulfonate salt. The expression in the above, 'a substituent having the group', means a substituent having not more than 20 carbon atoms. These substituents include, for example, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted alkylamido group, a substituted or unsubstituted alkylcarbamoyl group, a substituted or unsubstituted alkylsulfonamido group and a substituted or unsubstituted alkylsulfamoyl group. In Formula (1), the alkyl groups represented by Z include, preferably, those having from 1 to 30 carbon atoms and, particularly, a straight-chained, branched or cyclic alkyl group having from 2 to 20 carbon atoms, provided that the alkyl groups may also have other substituents than the above-given substituents. The aromatic groups represented by Z are preferably those of the monocyclic or condensed ring type having from 6 to 32 carbon atoms, provided that they may also have other substituents than the above-given substituents. The heterocyclic groups represented by Z include, preferably, those of the monocyclic or condensed ring type having from 1 to 32 carbon atoms, and they have each 5- or 6-membered ring and from 1 to 6 hetero atoms selected independently from nitrogen, oxygen and sulfur atoms, provided that they may also have other substituents than the above-given substituents. In Formula (1), the ammonio group has as a substituent a substituted or unsubstituted straight-chained, branched or cyclic alkyl group (such as a methyl, ethyl, benzyl, ethoxypropyl or cyclohexyl group), a substituted or unsubstituted phenyl group or naphthyl group and the substituent has preferably 20 or less carbon atoms. Among the compounds represented by Formula (1), those particularly preferred include, for example, those represented by the following Formulae (1-a), (1-b) and (1-c). These compounds are described in JP OPI Publication Nos. 56-72441/1981, 56-24347/1981, 60-122642/1985, 60-258537/1985 and 4-29233/1992. However, there is no disclosure of the effects obtainable when a light-sensitive material containing a hydrazine derivative is developed with such a developer to which these compounds are added, and the developer is replenished in a replenishing amount of not more than 200 ml/liter. wherein T represents an atomic group necessary to form a 5-membered heterocyclic ring; J represents a hydroxy group, -SO 3 M 1 , -COOM 1 (in which M 1 is synonymous with M 1 denoted in Formula (1)), a substituted or unsubstituted amino group or a substituted or unsubstituted ammonio group, or an alkylthio group having from 1 to 19 carbon atoms, an alkylamido group having from 2 to 18 carbon atoms, an alkylcarbamoyl group having from 2 to 18 carbon atoms, an alkyl group having from 1 to 19 carbon atoms or an aromatic group having from 6 to 31 carbon atoms, each substituted with one or more of the above-given groups; and M is synonymous with M denoted in Formula (1). Formula (1-b) A 1 -ALK-SM 2 wherein A 1 represents a hydroxy group, -SO 3 M 1 , -COOM 1 (in which M 1 is synonymous with M 1 denoted in Formula (1)), a -N(R 3 ) 2 group (in which R 3 represents a substituted or unsubstituted alkyl group having from 1 to 5 carbon atoms, provided that a ring may be formed by linking two R 3 substituents to each other); ALK represents a substituted or unsubstituted alkylene group having from 2 to 12 carbon atoms; and M 2 represents a hydrogen atom or the following group: wherein R 4 represents a hydrogen atom, a substituted or unsubstituted alkyl group having from 1 to 5 carbon atoms, or a substituted or unsubstituted phenyl group having not more than 10 carbon atoms; X - represents a halide ion or sulfonic acid ion, or a -S-ALK-A 1 group. Formula (1-c) A 1 -Ar-SM wherein A 1 is synonymous with A 1 denoted in Formula (1-b); Ar represents an aryl group that may be substituted; and M is synonymous with M denoted in Formula (1). Typical examples of the compounds represented by Formula (1) will be given below. It is, however, to be understood that the invention shall not be limited thereto. (1-21) HS-CH 2 -CH 2 -COOH (1-22) NaS-CH 2 -CH 2 -SO 3 Na Now, Formula (2) will be detailed below. wherein A 1 and A 2 independently represent an aliphatic group, an alicyclic group, an aralkyl group, an aryl group, or a 5 or 6-membered heterocyclic group having hydrogen atom or a substituent; m 1 and m 2 each represent 1, 2 or 3; n represents 1 or 2; and B 1 and B 2 independently represent -COOM, -SO 3 M', -CON(X) (Y), -S-Z' or -SO 2 N(X)(Y) wherein X and Y independently represent a hydrogen atom, an alkyl group having from 1 to 8 carbon atoms or an aryl group, either of which may have a hydroxy group, a carboxylic acid group or a sulfonic acid group; M' represents a monovalent cation; and Z' is synonymous with X and Y, provided that Z' is not a hydrogen atom. Among the compounds represented by Formula (2), preferred compounds may be represented by the following Formulae (2-a) and (2-b): In Formula (2-a), R 1 and R 3 each represent a hydrogen atom, an alkyl group having from 1 to 6 carbon atoms that may be substituted, an alkenyl group, an aralkyl group, a cycloalkyl group, a phenyl group that may be substituted, a 5- or 6-membered heterocyclic ring containing from 1 to 3 nitrogen atoms, an oxygen atom or a sulfur atom, or a carboxylic acid group; R 2 represents a direct bond, an alkylene group that may be substituted, an alkylidene group, a phenylene group, an aralkylene group or -CONHCH2-; A 3 represents -COOM or -SO 3 M (in which M is synonymous with M 1 denoted in Formula (1)); and m 2 is 1 or 2.) In Formula (2-b), R 4 and R 5 represent each a hydrogen atom or a methyl group; and M preferably represents a hydrogen cation or an alkali-metal ion (such as Na + or K + ). Among the compounds represented by Formula (2-a), the compounds represented by Formula (2-a-1) are preferable. In Formula (2-a-1), R 6 and R 7 each represent a hydrogen atom, an alkyl group that may be substituted (such as -CH 3 , -C 2 H 5 , -CH 2 OH, and -CH 2 COOH), a cycloalkyl group (such as a cyclopentyl group and a cyclohexyl group), a phenyl group that may be substituted (such as a phenyl group, a tolyl group, a p-chlorophenyl group, an aminophenyl group, a p-sulfophenyl group and a p-sulfonamidophenyl group), a 5- or 6-membered heterocyclic ring containing 1 to 3 nitrogen atoms, an oxygen atom or a sulfur atom (such as a furyl group and a thienyl group), or a carboxylic acid group, provided, R 6 and R 7 may be the same or different; and ℓ is 1, 2, 3 or 4. These compounds are disclosed in JP OPI Publication No. 4-29233/1992. However, the effects of the developers for light-sensitive materials containing a hydrazine derivative as a contrast hardener have not yet been disclosed. Typical examples of the compounds represented by Formula (2) will be given below: (2-3) HOOC-H 2 C-S-S-CH 2 -COOH (2-8) Thiolactic acid (2-9) α-mercaptoisobutyric acid (2-11) HOOC(CH 2 ) 2 -S-S-(CH 2 ) 2 COOH (2-12) HOOC(CH 2 ) 3 -S-S-(CH 2 ) 3 COOH (2-33) HOOC-CH 2 -S-S-S-CH 2 -COOH The compounds represented by Formula (1) or (2) may be used preferably in an amount within the range of from 0.1 millimols to 10 millimols per liter of developer used. The black-and-white silver halide photographic light-sensitive materials used in the method of the invention are processed through an automatic processor. In processing them, they are processed while replenishing a developer in a specific amount in proportion to the area of the light-sensitive material processed. The amount of the developer to be replenished is to be not more than 200 ml and, preferably, within the range of not less than 75 ml to not more than 200 ml per m 2 of the light-sensitive material so that waste developer can be reduced. If the amount of the developer replenished is less than 75 ml, any satisfactory photographic characteristics cannot be obtained, due to the desensitization, softened contrast and so forth. In view of shortening developing time, when a film is processed through an automatic processor, the whole processing time (dry to dry time) is preferably within the range of from 20 to 60 seconds from the time when the leading edge of the film is inserted into the automatic processor to the time when the leading edge thereof is delivered out of the drying zone of the automatic processor. The expression, 'the whole processing time' stated herein include the time for completing all of the processing steps required for processing a black-and-white silver halide photographic light-sensitive material, such as, typically, the time required for completing the steps of developing, fixing, bleaching, washing, stabilizing, drying and so forth, that is so-called dry to dry time. If the whole processing time is shorter than 20 seconds, any satisfactory photographic characteristics cannot be obtained, due to desensitization, softened contrast and so forth. It is further preferable that the whole processing time (dry to dry time) is within the range of from 30 to 60 seconds. Hydrazine derivatives useful in the method of the invention include, preferably, the compounds represented by the following Formula (H): wherein A represents an aryl group or a heterocyclic group containing at least one sulfur or oxygen atom; G represents a group, a sulfonyl group, a sulfoxy group, group, or an iminomethylene group; n is 1 or 2; A 1 and A 2 each represent a hydrogen atom, or one of them represents a hydrogen atom and the other represents a substituted or non-substituted alkylsulfonyl or acyl group; R represents a hydrogen atom or an alkyl, aryl, alkoxy, aryloxy, amino, carbamoyl, oxycarbonyl or -O-R 2 group in which R 2 represents an alkyl or saturated heterocyclic group. Among these compounds, the compounds represented by the following Formula (H-c) or (H-d) are further preferable in the invention: wherein A represents an aryl group or a heterocyclic group containing at least one sulfur or oxygen atom; n is 1 or 2 and, when n is 1, R 15 and R 16 each represent a hydrogen atom, an alkyl, alkenyl, alkinyl, aryl, heterocyclic, hydroxy, alkoxy, alkenyloxy, alkinyloxy, aryloxy or heterocyclic-oxy group, provided that, R 15 and R 16 may form a ring together with a nitrogen atom and, when n is 2, R 15 and R 16 each represent a hydrogen atom, an alkyl, alkenyl, alkinyl, aryl, saturated or unsaturated heterocyclic, hydroxy, alkoxy, alkenyloxy, alkinyloxy, aryloxy or heterocyclic-oxy group, provided that when n is 2, at least one of R 15 and R 16 represents an alkenyl, alkinyl, saturated heterocyclic, hydroxy, alkoxy, alkenyloxy, alkinyloxy, aryloxy or heterocyclic-oxy group; and R 17 represents an alkyl, alkenyl, aryl, alkinyl or heterocyclic group. The compounds represented by Formula (H-c) or (H-d) include the compounds in which at least one of the two Hs denoted in -NHNH- of the Formula is substituted by a substituent. In particular, A represents an aryl group (such as a phenyl or naphthyl group), or a heterocyclic group containing at least one of sulfur or oxygen atoms (such as a thiophene, furan, benzothiophene or pyrane group). R 15 and R 16 each represent a hydrogen atom, an alkyl group (including, for example, a methyl, ethyl, methoxyethyl, cyanoethyl, hydroxyethyl, benzyl or trifluoroethyl group), an alkenyl group (including, for example, an allyl, butenyl, pentenyl or pentadienyl group), an alkinyl group (including, for example, a propargyl, butynyl or pentenyl group), an aryl group (including, for example, a phenyl, naphthyl, cyanophenyl or methoxyphenyl group), a heterocyclic group (including, for example, an unsaturated heterocyclic group such as a pyridine, thiophene or furan group and a saturated heterocyclic group such as a tetrahydrofuran or sulfolane group), a hydroxy group, an alkoxy group (including, for example, a methoxy, ethoxy, benzyloxy or cyanomethoxy group), an alkenyloxy group (including, for example, an allyloxy or butenyloxy group), an alkinyloxy group (including, for example, a propargyloxy or butynyloxy group), an aryloxy group (including, for example, a phenoxy or naphthyloxy group), or a heterocyclic-oxy group (including, for example, a pyridyloxy or pyrimidyloxy group); provided that when n is 1, R 15 and R 16 may form a ring (such as a piperidine, piperazine or morpholine ring) together with a nitrogen atom. Provided that when n is 2, at least one of R 15 and R 16 represents an alkenyl, alkinyl, saturated heterocyclic, hydroxy, alkoxy, alkenyloxy, alkinyloxy, aryloxy or heterocyclic-oxy group. Suitable examples of the alkyl, alkenyl, aryl, alkinyl groups or heterocyclic groups each represented by R 17 include those given above. Into the aryl group, or the heterocyclic group having at least one sulfur or oxygen atom, represented by A, a variety of substituents may be introduced. The substituents which can be introduced thereinto include, for example, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, an alkylthio group, an arylthio group, a sulfonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfamoyl group, an acyl group, an amino group, an alkylamino group, an arylamino group, an acylamino group, a sulfonamido group, an arylaminothiocarbonylamino group, a hydroxy group, a carboxy group, a sulfo group, a nitro group and a cyano group. Among these substituents, a sulfonamido group is preferable. In each of the formulae, A is preferable to contain at least one of antidiffusible groups or silver halide adsorption accelerating groups. The antidiffusible groups include, preferably, a ballast group commonly applicable to immobile photographic additives such as couplers. The ballast groups are relatively inert groups having not less than 8 carbon atoms, and they may be selected, for example, from an alkyl group, a phenyl group, an alkylphenyl group, a phenoxy group, an alkylphenoxy group and so forth. The silver halide adsorption accelerating groups include, for example, those given in U.S. Patent No. 4,385,108, such as a thiourea group, a thiourethane group, a heterocyclic thioamido group, a mercaptoheterocyclic group and a triazole group. A hydrogen of the -NHNH- of Formulae (H-c) and (H-d), that is, a hydrogen atom contained in hydrazine, may also be substituted with substituents including, for example, a sulfonyl group (such as a methanesulfonyl or toluenesulfonyl group), an acyl group (such as an acetyl, trifluoroacetyl or ethoxycarbonyl group), and an oxalyl group (such as an ethoxalyl or pyruvoyl group). The compounds represented by Formulae (H-c) and (H-d) include such compounds as mentioned above. Further preferable compounds include, for example, those where n is 2 in Formula (H-c). In the compounds where n is 2 in Formula (H-c), it is further preferable that R 15 and R 16 each represent a hydrogen atom, an alkyl group, an alkenyl group, an alkinyl group, an aryl group, a saturated or unsaturated heterocyclic group, a hydroxy group or an alkoxy group, and at least one of R 31 and R 32 represents an alkenyl group, an alkinyl group, a saturated heterocyclic group, a hydroxy group or an alkoxy group. Compounds represented by the foregoing Formulae (H-c) and (H-d) include the following compounds. However, the invention is not limited to the use of these compounds. Examples of the concrete compounds include the following: Other examples include, for example, compounds (1) to (61) and (65) to (75) given in JP OPI Publication No. 2-841/1990, pp.542(4) ~ 546(8). The hydrazine derivatives useful in the method of the invention may be synthesized in the process described in JP OPI Publication No.2-841/1990, pp.546(8) ~ 550(12). The hydrazine derivatives useful in the method of the invention are added to silver halide emulsion layers and/or the layers adjacent thereto. These derivatives are to be added in an amount within the range of, preferably, from 1x10 -6 mols to 1x10 -1 mols and, particularly, from 1x10 -5 mols to 1x10 -2 mols per mol of silver. When the hydrazine derivatives comprise the compounds represented by Formula (H-c) or (H-d), it is preferable to contain at least one nucleation accelerating compound as described in JP OPI Publication No. 4-98239/1992, the 1st line of the upper left column on p. (7) to the 11th line of the lower left column of p.(26), into a silver halide emulsion layer and/or a non-light-sensitive layer arranged to the silver halide emulsion layer side of a support. Examples of suitable nucleation accelerating compounds will be given below: Further examples thereof are also given in the following examples of nucleation accelerating compounds; namely; compounds I-1 ~ I-26 given in JP OPI Publication No. 4-98239/1992, p.(8); compounds II-1 ~ II-29 given in, ibid., pp.(9)~(10); compounds III-1 ~ III-25 given in, ibid., pp.(10)~(11); compounds IV-1 ~ IV-41 given in, ibid., pp.84~90; compounds V-I-1 ~ V-I-27 given in, ibid., pp.(11)~(13); compounds V-II-1 ~ V-II-30 given in, ibid., pp.(13)~(14); compound V-III-35 given in, ibid., p.(16); compounds VI-I-1 ~ VI-I-44 given in, ibid., pp.(18)~(20); compounds VI-II-1 ~ VI-II-68 given in, ibid., pp. (21)~(24); and compounds VI-III-1 ~ VI-III-35 given in, ibid., pp.(24)~(26) Besides the compounds defined above, the following additives may also be added to the developers of the invention. Namely, inorganic development inhibitors such as potassium bromide; organic development inhibitors such as 5-methylbenzotriazole, 5-methylbenzimidazole, 5-nitroindazole, adenine, guanine and 1-phenyl-5-mercaptotetrazole; metal-ion scavengers such as ethylenediamine tetraacetic acid; development accelerators such as methanol, ethanol, benzyl alcohol and polyalkylene oxide; surfactants such as sodium alkylarylsulfonate, natural saponin, sugar and the alkyl esters of the foregoing compounds; layer hardeners such as glutaraldehyde, formalin and glyoxal; ionic strength controllers such as sodium sulfate. Developers useful in the method of the invention may also contain glycols such as diethylene glycol and triethylene glycol to serve as an organic solvent. It is however preferable that the developers may not contain any alkanolamines in such an amount that a hard contrast is provided. In each of the silver halide emulsions useful in the method of the invention (hereinafter referred to as "a silver halide emulsion" or simply "an emulsion"), it is allowed to use arbitrary silver halides applicable to any common silver halide emulsions, for example, silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide and silver chloride. Among these silver halides, silver chlorobromide, silver bromide, or silver iodobromide or silver iodochlorobromide each having a silver iodide content of not more than 2 mol% are preferable. It is further preferable to use monodisperse type grains each having a variation coefficient of not more than 15%. The above-mentioned variation coefficient is represented by the following equation: (Standard deviation of grain size)/(Average grain size) x 100 The silver halide emulsions of the invention can be applied with a variety of techniques, additives and so forth which have been well-known in the art. For example, the silver halide photographic emulsions and the backing layers can contain a variety of chemical sensitizers, color toners, layer hardeners, surfactants, thickeners, plasticizers, lubricants, development inhibitors, UV absorbents, anti-irradiation dyes, heavy metals, matting agents and so forth, in various methods. Further, the silver halide photographic emulsions and backing layers can also contain polymer latexes. The above-mentioned additives are further detailed in Research Disclosure, Vol.176, Item/7643, Dec., 1978 and, ibid., Vol.187, Item/8716, Nov., 1979. The corresponding pages and columns thereto will be collectively given below. Kind of Additive RD/7643 RD/8716 1. Chemical sensitizer p.23 p.648, r.col. 2. Sensitivity raiser -ditto- 3. Spectral sensitizer Supersensitizer pp.23~24 p.648, r.col. p.649, r.col. 4. Whitening agent p.24 5. Antifoggant & stabilizer pp.24~25 p.649, r.col. 6. Light absorbent, filter dye UV absorbent pp.25~26 p.649, r.col. p.650, l.col. 7. Antistaining agent p.25, r.col. p.650, l-r.cols. 8. Dye image stabilizer p.25 9. Layer hardener p.26 p.651, l.col. 10. Binder p.26 -ditto- 11. Plasticizer & lubricant p.27 p.650, r.col. 12. Coating aid & surfactant pp.26~27 -ditto- 13. Antistatic agent p.27 -ditto- Suitable supports for the silver halide photographic light-sensitive materials useful in the method of the invention include, for example, those made polyester, such as cellulose acetate, cellulose nitrate and polyethyleneterephthalate; those made of polyethylene, such as polyolefin; polystyrene; baryta paper; polyolefin-coated paper; glass plate; metal plate; and so forth. These supports may also be sub-treated if required. EXAMPLES Some concrete examples of the invention will be detailed below. However, the embodiments of the invention shall not be limited thereto. Example 1 (Preparation of silver halide photographic emulsion A) A silver iodobromide emulsion (having a silver iodide content of 0.7 mol% per mol of silver) was prepared in a double-jet precipitation process. In the process, K 2 IrCl 6 was added in an amount of 8x10 -7 mols per mol of silver. The resulting emulsion was proved to be an emulsion comprising cubic-shaped monodisperse type grains having an average grain size of 0.20µm (with a variation coefficient of 9%). After adding SD-1 in an amount of 8mg/m 2 thereto, the resulting matter was washed with water and then desalted in ordinary methods. The resulting pAg thereof was 8.0 at 40°C after completing the desalting treatment. Successively, an aqueous potassium iodide solution was added in an amount of 0.1 mol% per mol of silver into the resulting emulsion and the surfaces of the grains were each subjected to a conversion treatment. After that, the mixture of compounds (A), (B) and (C) was added and a sulfur sensitization was then applied thereto, so that emulsion A was prepared. (Preparation of silver halide photographic light-sensitive material) A 100µm-thick polyethylene terephthalate film was coated on both sides thereof respectively with 0.1µm-thick sublayers (refer to Example 1 given in JP OPI Publication No. 59-19941/1984). Onto one of the sublayers, a silver halide emulsion layer having the following chemical prescription (1) was so coated as to have a gelatin content of 2.0 g/m 2 and a silver content of 3.2 g/m 2 . Onto the emulsion layer, an emulsion protective layer having the following chemical prescription (2) was so coated as to have a gelatin content of 1.0 g/m 2 . On to the other sublayer on the opposite side, a backing layer having the following chemical prescription (3) was so coated as to have a gelatin content of 2.4 g/m 2 . Further, onto the backing layer, a backing protective layer having the following chemical prescription (4) was so coated as to have a gelatin content of 1 g/m 2 . Resultingly, a sample was prepared. (Evaluation of silver sludge (silver contamination)) The resulting sample was exposed to an Ar laser beam for 10 -6 seconds and the exposed sample was processed under condition described later with an automatic processor (manufactured by Konica Corp.) for rapid-processing use into which developer 1 and fixer having the composition described later are introduced, under the conditions of replenishing the developer in an amount of 160 mℓ and the fixer in an amount of 190mℓ, each per m 2 of the sample. A process in which 200 film sheets per day, each measuring 508 × 610 mm were developed under the above-mentioned conditions was repeated for three days. After that, an unexposed film sheet measuring 508 × 610 mm was developed through the automatic processor and a roller-streak like silver contamination was observed on the film surface. After development was carried out for three days in the same manner as mentioned above, the automatic processor is stopped and, after 24 hours, black silver contamination produced in the developer tank of the automatic processor was observed. The evaluation was carried out as follows: Rank 5: No silver contamination produced, Rank 4: Faint silver contamination produced, Rank 3: Slight silver contamination produced, Rank 2: Silver contamination produced, and Rank 1: Much silver contamination produced. In ranks lower than Rank 2, there is a problem in practical application. (Evaluation of photographic characteristics) The resulting sample was brought into close contact with a wedge and exposed to an Ar laser beam for 10 -6 seconds. The exposed sample was then processed with an automatic processor for rapid processing use, Model GR-26SR manufactured by Konica Corp., into which developer and fixer were introduced under the following conditions, using a developer having the composition described below and standing ten days after preparation and using a fixer having the composition described below. The density of the resulting sample was measured through an optical densitometer, Konica Model PDA-65. The measured sensitivity of the sample was indicated by a sensitivity relative to the sensitivity of Sample No.1 having a density of 2.5 which was regarded as a standard value of 100, and the gamma value of the sample was indicated by a tangent between the densities of 0.1 and 2.5. When the gamma value was not less than 8.0, the resulting contrast was not satisfactory, and caused problems in practical use. (Evaluation of black spot) Of the resulting processed samples, the unexposed areas thereof were each evaluated with the eye through a 40X magnifier. The samples having no black spot were evaluated as the highest rank '5' and graded as ranks '4', '3', '2' and '1' respectively from the second rank to the lowest rank in order of black spot production. Those graded as ranks '2' and '1' were not on the practically satisfactory level. (Composition of developer 1) Potassium sulfite See Table 1 Hydroquinone 20.0 g 4-methyl-4-hydroxymethyl-1-phenyl -3-pyrazolidone 1.0 g Disodium ethylenediamine tetraacetate 2.0 g Potassium carbonate 12.0 g Potassium bromide 5.0 g 5-methyl benzotriazole 0.3 g Diethylene glycol 25.0 g Compound of Formula (1) or (2) See Table 1 Add water to make 1 liter Adjust pH with potassium hydroxide to be pH 10.7 Chemical formula of fixer Ammonium thiosulfate (in an aqueous 72.5% W/V solution) 200 ml Sodium sulfite 17 g Sodium acetate, trihydrate 6.5 g Boric acid 6.0 g Sodium citrate, dihydrate 2.0 g Pure water (ion-exchange water) 17 ml Sulfuric acid (in an aqueous 50% W/V solution) 2.0 g Aluminum sulfate (in an aqueous 8.1% W/V solution converted into an Al 2 O 3 content) 8.5 g Before using the fixer, water added to make 1 liter Adjust pH with acetic acid to be pH 4.8 (Processing condition) Processing time included the cross-over time. (Processing step) (Temperature) (Time) Developing 38°C 12 sec. Fixing 35°C 10 sec. Washing 30°C 10 sec. Drying 50°C 13 sec. Total:45 sec. The results thereof will be given in Table 1. From the results shown in Table 1, it was proved that the samples of the invention produce no deterioration in both sensitivity and gamma and little silver sludge contamination, and inhibit any black spot production. Example 2 (Emulsion preparation) A silver nitrate solution and an aqueous solution containing sodium chloride, potassium bromide and rhodium hexachloride complex, in an amount of 8x10 -5 mols/mol of Ag were prepared. The resulting solutions were simultaneously added to a gelatin solution while controlling the flow rates of the two solutions and the mixture was desalted in an ordinary method. Thereby, a cubic, monodisperse type silver chlorobromide emulsion having an average grain size of 0.13µm and a silver bromide content of 1 mol% could be obtained. The resulting emulsion was sulfur-sensitized in an ordinary method and, thereto, 6-methyl-4-hydroxy-1,3,3a,7-tetrazaindene was added as a stabilizer. After that, the following additives were added to prepared an emulsion-coating solution. Next, an emulsion-protective layer coating solution, a backing layer coating solution and a backing layer-protective layer coating solution were each prepared so as to have the following compositions. In an nitrogen atmosphere, a mixed solution of (i) 3.0 kg of styrene, (ii) 3.0 kg of methyl methacrylate and (iii) 3.2 kg of ethyl acrylate and 0.8 kg of sodium 2-acrylamido-2-methylpropane sulfonate was added into a mixture solution containing 60 liters of water, 1.0 kg of gelatin, 0.01 kg of sodium dodecylbenzene sulfonate and 0.05 kg of ammonium persulfate over one hour while stirring at a solution temperature of 60°C. After that, the resulting solution was further stirred for another 1.5 hours and then vapor distilled for one hour so that the remaining monomers were removed. The solution was cooled to room temperature and the pH thereof was adjusted to 6.0 by making use of ammonia. The resulting latex solution was finished by adding water to make 75 kg. In the above-mentioned manner, a monodisperse type latex having an average particle size of 0.1µm was prepared. Each of the resulting coating solutions was multicoated on a 100µm-thick subbed polyethylene terephthalate support so as to provide a backing layer and a backing protective layer on the back side in this order from the position closer to the support, and they were dried. Next, the coating solutions were each multicoated on the support so as to provide an emulsion layer and an emulsion protective layer on the surface of the support opposite the backing layer side in this order from the position closer to the support and they were dried. The resulting samples were each evaluated in the same manner as in Example 1, except that the samples were each processed with the following developer 2. The results will be given in Table 2. (Composition of developer 2) Potassium sulfite See Table 2 Hydroquinone 25.0 g N-methyl-p-aminophenol-1/2-sulfate 0.8 g Disodium ethylenediamine tetraacetate 1.0 g Sodium carbonate 13.5 g L-sodium ascorbate 1.0 g Potassium bromide 6.0 g 5-methylbenzotriazole 0.4 g Diethyleneglycol 25.0 g Compound of Formula (1) or (2) See Table 2 Add water to make 1 liter Adjust pH with potassium hydroxide to be 10.3. From the results shown in Table 2, it was proved that the samples of the invention displayed the excellent results in every item same as in Example 1.

Claims: A method of developing with developer a black-and-white silver halide photographic light-sensitive material comprising a support and provided thereon, a silver halide photographic emulsion layer and a hydrophilic colloid layer other than the silver halide photographic emulsion layer, using an automatic processor, replenisher for developer being supplied to the developer in an amount of not more than 200 ml per m 2 of the material, at least one layer of the emulsion layer and the hydrophilic colloid layer comprising hydrazine derivative and a nucleation accelerating compound, the developer having a pH value of from 10.0 to 11.2 and comprising a dihydroxybenzene compound and either a 3-pyrazolidone compound or an aminophenol compound, from 0.3 to 1.2 mol/litre of a sulfite and at least one compound represented by the following Formulae (1) or (2): Formula (1) Z-SM wherein Z represents an alkyl, aryl and heterocyclic group having a group chosen from a hydroxy group, a -SO 3 M 1 group, a -COOM 1 group, a substituted or unsubstituted amino group and a substituted or unsubstituted ammonio group wherein M 1 represents a hydrogen atom, an alkali metal atom or a substituted or unsubstituted ammonium ion or a substituent having the group; and M represents a hydrogen atom, an alkali metal atom or a substituted or unsubstituted amidino group which may form a hydrogen halogenide or sulfonate salt, wherein A 1 and A 2 independently represent an aliphatic group, an alicyclic group, an aralkyl group, an aryl group, or a 5- or 6-membered heterocyclic group; m 1 and m 2 independently represent 1, 2 or 3; n represents 1 or 2; and B 1 and B 2 independently represent -COOM', -SO 3 M', -CON(X) (Y), -S-Z' or -SO 2 N(X) (Y) wherein X and Y each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms or an aryl group; M' represents a monovalent cation; and Z' represents an alkyl group having 1 to 8 carbon atoms or an aryl group. A method according to claim 1, wherein the total processing time is within the range of from 20 to 60 seconds. A method according to claims 1 or 2, wherein the developer comprises the dihydroxybenzene compound in an amount of from 0.05 to 1.5 mol/litre and the 3-pyrazolidone compound in an amount of not more than 0.2 mol/litre. A method according to any of claims 1 to 3, wherein the developer comprises the dihydroxybenzene compound in an amount of from 0.05 to 1.5 mol/litre and the aminophenol compound in an amount of not more than 0.2 mol/litre. A method according to any preceding claim, wherein the developer comprises at least one compound represented by Formulae (1) or (2) in an amount of from 0.1 to 10 mmol/litre. A method according to any preceding claim, wherein the developer has a pH of from 10.0 to 10.9. A method according to claim 6, wherein the developer has a pH of from 10.0 to 10.7. A method according to any preceding, wherein the developing comprises supplying replenisher for the developer in an amount of from 75 to 200 ml per m 2 of the material. A method according to any preceding claim, wherein at least one of the emulsion layer and the hydrophilic colloid layer comprises the hydrazine derivative in an amount of from 1 X 10 -6 to 1 X 10 -1 mol per mol of silver. A method according to any preceding claim, wherein the hydrazine derivative is a compound of Formula (H-c) or Formula (H-d): wherein A represents an aryl group or a heterocyclic group comprising at least one of a sulfur and oxygen atom; n represents 1 or 2; and when n is 1, R 15 and R 16 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkinyl group, an aryl group, a heterocyclic group, a hydroxy group, an alkoxy group, an alkenyloxy group, an alkinyloxy group, an aryloxy group or a heterocyclicoxy group, or R 15 and R 16 may form a ring together with a nitrogen atom; and when n is 2, R 15 and R 16 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkinyl group, an aryl group, a heterocyclic group, a hydroxy group, an alkoxy group, an alkenyloxy group, an alkinyloxy group, an aryloxy group or a heterocyclicoxy group, provided that at least one of R 15 and R 16 represents an alkenyl group, an alkinyl group, a saturated heterocyclic group, a hydroxy group, an alkoxy group, an alkenyloxy group, an alkinyloxy group, an aryloxy group or a heterocyclicoxy group, wherein R 17 represents an alkyl group, an alkenyl group, an aryl group, an alkinyl group, or a heterocyclic group. A method according to claim 10, wherein the hydrazine derivative is a compound of Formula (H-c): wherein A, R 15 , R 16 and n are as defined in claim 10.

Inventors: SANPEI TAKESHI, SANPEI, TAKESHI
Applicants: KONISHIROKU PHOTO IND, KONICA CORPORATION
Application year: 1993
Main classification: G03C5
IPC codes: G03C5, G03C1