Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
  • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
  • G03C5/29—Development processes or agents therefor
  • G03C5/31—Regeneration; Replenishers
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
  • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
  • G03C5/29—Development processes or agents therefor
  • G03C5/30—Developers

Definitions

• the present invention relates to a method for developing a silver halide photographic material (hereinafter referred to as a photographic material) which is used in the field of photomechanical processes, provides ultrahigh contrast and has reduced changes in photographic properties due to processing. Further, the present invention relates to a method for decreasing silver stain (also called silver sludge) adhered or precipitated to a photographic material, a development tank or roller of an automatic processor, and thus for facilitating routine maintenance of equipment and machinery.
• a silver stain also called silver sludge
• photographic processing waste liquid can not be discharged into sewerages as it is, and it is necessary to recover the waste liquid and to subject it to burning treatment. It has been therefore desired to reduce the replenishment rate of processing solutions when the photographic materials are processed by use of the automatic processors.
• a decrease in the replenishment rate of the developers raises the problems of deterioration of the stability of the photographic properties and adhesion of silver eluted from the photographic materials to the photographic materials to be processed, thereby staining images. This is called silver stain or silver sludge, and contaminates the automatic processors themselves. Accordingly, periodic cleaning and maintenance of the automatic processors are required.
• the developer using ascorbic acid or a derivative thereof is readily oxidized by air, and when oxidized, it produces an acid to lower the pH of the developer.
• the pH reduction of the developer deteriorates the activity of a nucleating agent to induce a reduction in contrast and D max , resulting in instability of the photographic properties. It is therefore difficult to decrease a replenishment rate of a developer using ascorbic acid or a derivative thereof.
• the above-described object has been achieved by providing a method for continuously developing an exposed silver halide photographic material containing a hydrazine derivative by an automatic processor, wherein the development is carried out by using a developer being substantially free from a dihydroxybenzene compound but containing an ascorbic acid and/or a derivative thereof as a developing agent, an aminophenol derivative as an auxiliary developing agent which exhibits a superadditive property and at least 0.5 mol/liter of a carbonate as a buffer, and wherein the developer is replenished with a developing replenisher having a pH at least 0.2 higher than that of the starting developing solution.
• the developing replenisher for use in the present invention preferably contains a compound represented by the following general formula (1): wherein Z 1 represents a non-metallic atom group necessary to form a 5- or 6-membered nitrogen-containing aromatic heterocyclic ring together with the N and C atoms in general formula (1) and has R 1 and (SX 2 ) n as substituent groups, wherein R 1 represents a hydrogen atom, a halogen atom or a substituent group connected to the ring by a carbon atom, an oxygen atom, a nitrogen atom or a sulfur atom, X 1 and X 2 each represents a hydrogen atom or a cation, n is an integer of 0, 1 or 2, and two radicals each formed by eliminating any one hydrogen atom from Z 1 may combine to form a bis form structure.
• Z 1 represents a non-metallic atom group necessary to form a 5- or 6-membered nitrogen-containing aromatic heterocyclic ring together with the N and C atoms in general formula (1) and has R 1 and (SX
• Z 1 represents a non-metallic atom group necessary to form a 5- or 6-membered nitrogen-containing aromatic heterocyclic ring together with the N and C atoms in general formula (1).
• the 5-membered nitrogen-containing aromatic heterocyclic ring comprising Z 1 , N and C is formed by combination of an element selected from carbon, oxygen and sulfur, in addition to nitrogen, and may be condensed with a hydrocarbon ring or a hetero-cyclic ring.
• Such rings include pyrazole, imidazole, oxazole, thiazole, triazole, thiadiazole, oxa-diazole, indazole, benzimidazole, benzoxazole, benzothiazole, pyrazolotriazole and pyrrolotriazole.
• the 5-membered nitrogen-containing aromatic heterocyclic ring is preferably triazole, thiadiazole, oxadiazole, benzimidazole, benz-oxazole, benzothiazole, pyrazolotriazole or pyrrolotriazole, more preferably triazole, thiadiazole, oxadiazole or benz-imidazole, and most preferably triazole.
• the 6-membered nitrogen-containing aromatic heterocyclic ring comprising Z 1 , N and C is a monocyclic ring or a condensed ring formed by condensation with a carbon ring or a heterocyclic ring.
• examples of such rings include pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, phthalazine, quinoxaline, quinazoline, cinnoline, phenanthridine, phenanthroline, naphthyridine, pteridine, purine, triazolopyrimidine, imidazolopyridine, triazolopyridine, imidazolotriazine and triazolotriazine.
• the 6-membered nitrogen-containing aromatic heterocyclic ring is preferably pyrazine, pyrimidine, pyridazine, triazine, phthalazine, quinoxaline, quinazoline, naphthyridine, pteridine, purine, triazolopyrimidine, imidazolopyridine, triazolopyridine, imidazolotriazine or triazolotriazine, more preferably pyrimidine, pyridazine, triazine, pteridine, purine, triazolopyrimidine, imidazolotriazine or triazolotriazine, and most preferably pyrimidine, triazine or purine.
• R 1 represents a hydrogen atom, a halogen atom or a substituent group connected to the ring by a carbon atom, an oxygen atom, a nitrogen atom or a sulfur atom.
• substituent group connected by a carbon atom include alkyl, alkenyl, alkynyl, aryl, carbamoyl, alkoxycarbonyl, aryloxy-carbonyl, acyl, carboxyl, cyano and heterocyclic groups.
• Examples of those connected by an oxygen atom include hydroxyl, alkoxyl, aryloxy, heterocyclic oxy, acyloxy, carbamoyloxy and sulfonyloxy groups.
• Examples of those connected by a nitrogen atom include acylamino, amino, alkylamino, arylamino, heterocyclic amino, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonamido, imido and heterocyclic groups.
• Examples of those connected by a sulfur atom include alkylthio, arylthio, heterocyclic thio, sulfamoyl, alkoxysulfonyl, aryloxysulfonyl, sulfonyl, sulfo and sulfinyl groups. These groups may be further substituted by the group described as R 1 .
• Z 1 may have a plurality of R 1 groups, and two R 1 groups may combine to form a ring if necessary.
• the halogen atom is, for example, a fluorine atom, a chlorine atom or a bromine atom.
• the alkyl group is a straight chain, branched chain or cyclic alkyl group having from 1 to 10 carbon atoms, preferably from 1 to 5 carbon atoms, such as methyl, ethyl, isopropyl, t-butyl, benzyl and cyclopentyl.
• the alkenyl group is a group having from 2 to 10 carbon atoms, and examples of such groups include vinyl, 1-propenyl, 1-hexenyl and styryl.
• the alkynyl group is a group having from 2 to 10 carbon atoms, and examples of such groups include ethynyl, 1-butynyl and phenylethynyl.
• the aryl group is a group having from 6 to 10 carbon atoms, such as phenyl, naphthyl and p-methoxyphenyl.
• the carbamoyl group is a group having from 1 to 8 carbon atoms, such as carbamoyl, N-ethylcarbamoyl and N-phenyl-carbamoyl.
• the alkoxycarbonyl group is a group having from 2 to 8 carbon atoms, such as methoxycarbonyl and benzyloxycarbonyl.
• the aryloxycarbonyl group is a group having from 7 to 12 carbon atoms, such as phenoxycarbonyl.
• the acyl group is a group having from 1 to 8 carbon atoms, such as acetyl and benzoyl.
• the heterocyclic group connected to the ring by a carbon atom is a 5- or 6-membered saturated or unsaturated heterocyclic ring having from 1 to 5 carbon atoms and containing at least one oxygen atom, nitrogen atom or sulfur atom.
• the number and the kind of the hetero atom constituting the ring may be one or more, and examples of such groups include 2-furyl, 2-thienyl, 2-pyridyl and 2-imidazolyl.
• the alkoxyl group is a group having from 1 to 10 carbon atoms, preferably from 1 to 6 carbon atoms, such as methoxy, 2-methoxyethoxy and 2-methanesulfonylethoxy.
• the aryloxy group is a group having from 6 to 12 carbon atoms, such as phenoxy, p-methoxyphenoxy and m-(3-hydroxy-propionamido)phenoxy.
• the heterocyclic oxy group is a 5- or 6-membered saturated or unsaturated heterocyclic oxy group having from 1 to 5 carbon atoms and containing at least one oxygen atom, nitrogen atom or sulfur atom.
• the number and the kind of the hetero atom constituting the ring may be one or more, and examples of such groups include 1-phenyltetrazolyl-5-oxy, 2-tetrahydropyranyloxy and 2-pyridyloxy.
• the acyloxy group is a group having from 1 to 10 carbon atoms, preferably from 1 to 6 carbon atoms, such as acetoxy, benzoyloxy and 4-hydroxybutanoyloxy.
• the carbamoyloxy group is a group having from 1 to 10 carbon atoms, preferably from 1 to 6 carbon atoms, such as N,N-dimethyl-carbamoyloxy, N-butylcarbamoyloxy and N-phenylcarbamoyloxy.
• the sulfonyloxy group is a group having from 1 to 8 carbon atoms, such as methanesulfonyloxy and benzenesulfonyloxy.
• the acylamino group is a group having from 1 to 10 carbon atoms, preferably from 1 to 6 carbon atoms, such as acetylamino and benzoylamino.
• the alkylamino group is a group having from 1 to 10 carbon atoms, preferably from 1 to 6 carbon atoms, such as N,N-dimethylamino, N-(2-hydroxyethyl)amino and N-(3-dimethylamino-propyl)amino.
• the arylamino group is a group having from 6 to 10 carbon atoms, such as anilino and N-methylanilino.
• the heterocyclic amino group is a 5- or 6-membered saturated or unsaturated heterocyclic amino group having from 1 to 5 carbon atoms and containing at least one oxygen atom, nitrogen atom or sulfur atom.
• the number and the kind of the hetero atom constituting the ring may be one or more, and examples of such groups include 2-oxazolylamino, 2-tetra-hydrosopyranylamino and 4-pyridylamino.
• the ureido group is a group having from 1 to 10 carbon atoms, preferably from 1 to 6 carbon atoms, such as ureido, methylureido, N,N-diethylureido and 2-methanesulfonamidoethylureido.
• the sulfamoylamino group is a group having from 0 to 10 carbon atoms, preferably from 0 to 5 carbon atoms, such as methylsulfamoylamino and 2-methoxyethylsulfamoylamino.
• the alkoxycarbonylamino group is a group having from 2 to 10 carbon atoms, preferably from 2 to 6 carbon atoms, such as methoxycarbonylamino.
• the aryloxycarbonylamino group is a group having from 7 to 12 carbon atoms, such as phenoxycarbonylamino and 2,6-dimethoxyphenoxycarbonylamino.
• the sulfonamido group is a group having from 1 to 10 carbon atoms, preferably from 1 to 6 carbon atoms, such as methanesulfonamido and p-toluenesulfonamido.
• the imido group is a group having from 4 to 10 carbon atoms, such as N-succinimido and N-phthalimido.
• the heterocyclic group connected to the ring by a nitrogen atom is a 5- or 6-membered heterocyclic ring comprising a nitrogen atom and at least one of a carbon atom, an oxygen atom and a sulfur atom. Examples of such groups include pyrrolidino, morpholino and imidazolino.
• the alkylthio group is a group having from 1 to 10 carbon atoms, preferably from 1 to 5 carbon atoms, such as methylthio and 2-carboxyethylthio.
• the arylthio group is a group having from 6 to 12 carbon atoms, such as phenylthio and 2-carboxyphenylthio.
• the heterocyclic thio group is a 5-or 6-membered saturated or unsaturated heterocyclic thio group having from 1 to 5 carbon atoms and containing at least one of an oxygen atom, a nitrogen atom and a sulfur atom.
• the number and the kind of the hetero atom constituting the ring may be one or more, and examples of such groups include 2-benzothiazolylthio and 2-pyridylthio.
• the sulfamoyl group is a group having from 0 to 10 carbon atoms, preferably from 0 to 6 carbon atoms, such as sulfamoyl, methylsulfamoyl and phenylsulfamoyl.
• the alkoxysulfonyl group is a group having from 1 to 10 carbon atoms, preferably from 1 to 6 carbon atoms, such as methoxysulfonyl.
• the aryloxysulfonyl group is a group having from 6 to 12 carbon atoms, preferably from 6 to 10 carbon atoms, such as phenoxysulfonyl.
• the sulfonyl group is a group having from 1 to 10 carbon atoms, preferably from 1 to 6 carbon atoms, such as methanesulfonyl and benzenesulfonyl.
• the sulfinyl group is a group having from 1 to 10 carbon atoms, preferably from 1 to 6 carbon atoms, such as methanesulfinyl and benzenesulfinyl.
• R 1 is preferably a hydrogen atom, an alkyl group, an aryl group, a carbamoyl group, an acyl group, a cyano group, an alkoxyl group, an aryloxy group, an amino group, an acylamino group, an ureido group, a sulfamoylamino group, a sulfonamido group, an alkylthio group, an arylthio group, a sulfamoyl group or a sulfonyl group, more preferably a hydrogen atom, an alkyl group, an alkoxyl group, an aryloxy group, an amino group, an acylamino group, an ureido group or an alkylthio group, and most preferably a hydrogen atom, an alkyl group, an alkoxyl group, an amino group or an alkylthio group.
• X 1 and X 2 each represents a hydrogen atom or an cation.
• the cation is, for example, sodium, potassium, lithium, calcium, ammonium, tetrabutylammonium or triethylammonium.
• Preferred examples of X 1 and X 2 include a hydrogen atom, sodium, potassium and ammonium.
• n is preferably 1 or 2.
• the compound having a bis form structure formed by connecting two radicals which may be the same or different and each is formed by eliminating any one hydrogen atom from general formula (1) is preferably a compound represented by the following general formula (2): wherein Z 21 and Z 22 each represents a group represented by Z 1 of general formula (1) in which one hydrogen atom is eliminated therefrom, and X 21 and X 22 have the same meaning as defined for X 1 . Preferred examples thereof are the same as with the above respective group of general formula (1).
• L 2 is a divalent connecting group (an alkylene group, an alkenylene group, an alkynylene group, an arylene group, a divalent heterocyclic group or the above described group connected through either alone or a combination of two or more of -O-, -S-, -NH-, -CO- and -SO 2 -.
• the alkylene group represented by L 2 is, for example, ethylene, trimethylene, pentamethylene, propylene, 2-butene-1,4-yl, 2-butine-1,4-yl or p-xylylene.
• the alkenylene group is, for example, ethene-1,2-yl.
• the alkynylene group is, for example, ethine-1,2-yl.
• the arylene group is, for example, phenylene.
• the divalent heterocyclic group is, for example, furan-1,4-diyl.
• L 2 is preferably an alkylene group, an -NH-(alkylene)-NH- group, an -O-(alkylene)-O- group, an -S-(alkylene)-S-group, an -NH-(alkylene)-CONH-(alkylene)-NH-group or an -NH-(alkylene)-O-(alkylene)-NH- group, and more preferably an -NH-(alkylene)-NH- group or an -O-(alkylene)-O-group.
• R 31 and X 31 have the same meanings as defined for R 1 and X 1 , respectively.
• R 31 is preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a hydroxyl group, an amino group which may be substituted, a mercapto group or an alkylthio group, more preferably a hydrogen atom, an alkyl group, a hydroxyl group, an amino group which may be substituted or a mercapto group, and most preferably a hydrogen atom, an alkyl group or a mercapto group.
• R 32 is a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a hydroxyl group or an amino group which may be substituted.
• R 32 is preferably a hydrogen atom, an alkyl group, a hydroxyl group or an amino group which may be substituted, and more preferably a hydrogen atom or an alkyl group.
• R 41 , R 42 and X 41 have the same meanings as defined for R 31 , R 32 and X 31 of general formula (3), respectively, and preferred examples thereof are also the same as those defined for the above respective group of general formula (3).
• R 51 and X 51 have the same meanings as defined for R 31 and X 31 of general formula (3), respectively.
• R 51 is preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a hydroxyl group, an amino group which may be substituted, a mercapto group or an alkylthio group, more preferably an alkyl group, an amino group which may be substituted, a mercapto group or an alkylthio group, and most preferably a mercapto group or an alkylthio group.
• R 61 , R 62 and X 61 have the same meanings as defined for R 31 , R 32 and X 31 of general formula (3), respectively.
• R 61 is preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a hydroxyl group, an amino group which may be substituted, a mercapto group or an alkylthio group, more preferably a hydroxyl group, an alkoxyl group, an amino group which may be substituted, a mercapto group or an alkylthio group, and most preferably a hydroxyl group, an amino group which may be substituted or mercapto group.
• R 62 is preferably a mercapto group.
• R 71 , R 72 and R 73 have the same meanings as defined for R 61 , R 62 and R 62 of general formula (6), respectively, and preferred examples thereof are also the same as those defined for the above respective group of general formula (6), with the proviso that at least one of those is a mercapto group. It is more preferred that R 73 is a mercapto group.
• R 81 , R 82 , R 83 and R 84 have the same meanings as defined for R 61 , R 62 , R 61 and R 62 of general formula (6), respectively, and preferred examples thereof are the same as those defined for the above respective group of general formula (6), with the proviso that at least one of those is a mercapto group.
• R 83 is most preferably an amino group which may be substituted or a hydrogen atom. It is more preferred that R 84 is a mercapto group.
• R 91 , R 92 and R 93 each has the same meaning as defined for R 61 of general formula (6), and preferred examples thereof are also the same as those defined for the above respective group of general formula (6), with the proviso that at least one of those is a mercapto group. It is more preferred that R 92 or R 93 is a mercapto group.
• R 101 to R 104 and X 101 have the same meanings as defined for R 1 and X 1 of general formula (1), respectively.
• R 101 to R 104 are each preferably a hydrogen atom, a sulfo group, a carboxyl group, a hydroxyl group or a sulfamoyl group, and more preferably a hydrogen atom or a sulfo group. It is most preferred that R 103 is a sulfo group.
• pyrimidine compounds represented by general formula (8) are particularly preferred. Of the pyrimidine compounds, preferred are those having two or three mercapto groups. Moreover, of such pyrimidine compounds having two or three mercapto groups, particularly preferred are those represented by the following general formula (I), (II) and (III).
• R 10 represents a mercapto group, a hydrogen atom or an arbitrary substituent group
• X represents a water-soluble group or a substituent substituted by a water-soluble group
• Y 1 represents a water-soluble group or a group substituted by a water-soluble group
• R 20 represents a hydrogen atom or an arbitrary substituent group
• Y 2 represents a water-soluble group or a group substituted by a water-soluble group
• R 30 represents a hydrogen atom or an arbitrary group.
• R 10 in general formula (I) and Y 1 in general formula (II) each is not a hydroxyl group.
• R 10 in general formula (I) represents a mercapto group, a hydrogen atom or an arbitrary substituent group, provided that it is not a hydroxyl group.
• R 10 is preferably a mercapto group, a hydrogen atom or a substituent having from 0 to 15 carbon atoms selected from hydroxyl, amino, alkyl, aryl, alkoxy, aryloxy, acylamino, sulfonamido, alkylthio, arylthio, alkylamino and arylamino.
• X in general formula (I) represents a water-soluble group or a substituent substituted by a water-soluble group.
• the water-soluble group is a salt of a carboxylic or sulfonic acid, a salt such as ammonio group, or a group containing a dissociative group which is partially or wholly dissociated in an alkaline developer.
• Examples thereof include a sulfo group (and salts thereof), a carboxyl group (and salts thereof), a hydroxyl group, a mercapto group, an amino group, an ammonio group, a sulfonamido group, an acylsulfamoyl group, a sulfonylsulfamoyl group, an active methine group, and groups containing one of these groups.
• the "active methine group” means a methyl group substituted by two electron attractive groups, and examples thereof include dicyanometyl, ⁇ -cyano- ⁇ -ethoxycarbonylmethyl and ⁇ -acetyl- ⁇ -ethoxycarbonylmethyl.
• the substituent represented by X in general formula (I) is the above described water-soluble group or a substituent substituted by the above described water-soluble group.
• substituent which is substituted by water-soluble group, include an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an acyloxy group, an (alkyl, aryl or heterocyclic) amino group, an acylamino group, a sulfonamido group, a ureido group, a thioureido group, an imido group, a sulfamoylamino group, an (alkyl, aryl or heterocyclic) thio group, an (alkyl or aryl) sulfonyl group, a sulfamoyl group and an amino group.
• alkyl group having from 1 to 10 carbon atoms (particularly, a methyl group substituted by an amino group), an aryl group, an aryloxy group, an (alkyl, aryl or heterocyclic) amino group, an (alkyl, aryl or heterocyclic) thio group.
• R 11 has the same meaning as R 10 in general formula (I), and also has the same preferred examples
• R 12 and R 13 may be the same or different and each represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, provided that at least one of R 12 and R 13 has at least one water-soluble group, wherein the water-soluble group has the same meaning as that of X in general formula (I), and preferred examples thereof include sulfo (and salts thereof), carboxyl (and salts thereof), hydroxyl and amino.
• R 12 and R 13 each is preferably an alkyl group or an aryl group.
• the alkyl group is preferably a substituted or unsubstituted alkyl group having from 1 to 4 carbon atoms, and the substituent is preferably a water-soluble group, particularly, a sulfo group (or a salt thereof), a carboxyl group (or a salt thereof), a hydroxyl group or an amino group.
• R 12 or R 13 represents an aryl group
• the aryl group is preferably a substituted or unsubstituted phenyl group having from 6 to 10 carbon atoms
• the substituent is preferably a water-soluble group, particularly, a sulfo group (or a salt thereof), a carboxyl group (or a salt thereof), a hydroxyl group or an amino group.
• R 12 and R 13 may combine with each other to form a cyclic structure. Further, an unsaturated heterocyclic ring may be formed by the cyclization.
• Y 1 in general formula (II) represents a water-soluble group or a substituent substituted by a water-soluble group, and has the same meaning as that of X in general formula (I), provided that it is not a hydroxyl group.
• R 20 represents a hydrogen atom or an arbitrary substituent.
• the substituent, which is substituted by a water-soluble group, represented by Y 1 include an alkyl group, an aryl group, a heterocyclic group (including nitrogen-containing heterocyclic groups substituted at the site of the nitrogen), an amino group, an (alkyl, aryl or heterocyclic) amino group, an (alkyl, aryl or heterocyclic) thio group, an alkoxy group and an aryloxy group.
• the water-soluble group has the same meaning as that of X in general formula (I), and preferred examples thereof include sulfo (and salts thereof), carboxyl (and salts thereof), hydroxyl and amino.
• Y 1 in general formula (II) is preferably an active methine group having from 3 to 8 carbon atoms, an alkyl or aryl group substituted by a water-soluble group having from 1 to 15 carbon atoms, an alkyl- or aryl- amino group substituted by a water-soluble group having from 1 to 10 carbon atoms, an alkyl- or aryl- thio group substituted by a water-soluble group having from 1 to 10 carbon atoms, an alkoxy or aryloxy group substituted by a water-soluble group having from 1 to 10 carbon atoms, wherein the water-soluble group is particularly preferably a sulfo group (or a salt thereof), a carboxyl group (or a salt thereof), a hydroxyl group or an amino group.
• Y 1 is particularly preferably an (alkyl, aryl or heterocyclic) amino group having from 1 to 10 carbon atoms and substituted by a hydroxyl group, a sulfo group (or a salt thereof) or a carboxyl group (or a salt thereof).
• Such particularly preferred groups are represented by an -N(R 01 )(R 02 ) group, wherein R 01 and R 02 have the same meaning as that of R 12 and R 13 in general formula (1-A), respectively, and each also has the same preferred examples.
• R 20 represents a hydrogen atom or an arbitrary substituent.
• the arbitrary group include those group by which the nitrogen-containing aromatic heterocyclic ring formed by Z 1 in general formula (1) may be substituted.
• R 20 is preferably a hydrogen atom or a substituent having from 0 to 15 carbon atoms selected from hydroxyl, amino, alkyl, aryl, alkoxy, aryloxy, acylamino, sulfonamido, alkylthio, arylthio, alkylamino, arylamino and hydroxylamino.
• R 20 is most preferably a hydrogen atom.
• Y 2 represents a water-soluble group or a substituent substituted by a water-soluble group
• R 30 represents a hydrogen atom or an arbitrary substituent.
• Y 2 and R 30 have the same meaning as that in Y 1 and R 20 , respectively, and each also has the same preferred examples.
• JP-A-4-301837 JP-A-5-61159, JP-A-6-230525, JP-A-58-169147, JP-A-62-56959, U.S. Patent 3,212,892, JP-A-3-53244, JP-A-3-282457, JP-A-5-61159, JP-A-5-303179, JP-A-4-362942, JP-B-46-11630 (the term "JP-B" as used herein means an "examined Japanese patent publication") JP-A-6-175302 and JP-A-6-258783.
• the addition amount thereof is preferably from 0.01 mmol to 10 mmol per liter of developer, and particularly preferably from 0.1 mmol to 5 mmol per liter.
• R 1 represents an aliphatic group, an aromatic group or a heterocyclic group
• R 2 represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxyl group, an aryloxy group, an amino group or a hydrazino group
• a 1 and A 2 both represent hydrogen atoms, or one of them 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.
• the aliphatic group represented by R 1 is preferably a substituted or unsubstituted, straight chain, branched chain or cyclic alkyl, alkenyl or alkynyl group having from 1 to 30 carbon atoms.
• the aromatic group represented by R 1 is a monocyclic or dicyclic aryl group, such as a benzene ring or a naphthalene ring.
• the heterocyclic group represented by R 1 is a monocyclic or dicyclic, aromatic or non-aromatic heterocyclic ring, and may be cyclocondensed with an aryl group to form a heteroaryl group. Examples thereof include pyridine, pyrimidine, imidazole, pyrazole, quinoline, isoquinoline, benzimidazole, thiazole and benzothiazole rings.
• R 1 is preferably an aryl group.
• R 1 may be substituted, and typical examples of the substituent include alkyl (including active methine), alkenyl, alkynyl, aryl, groups containing heterocyclic rings, groups containing quaternized nitrogen atom-containing heterocyclic rings (for example, pyridinio), hydroxyl, alkoxyl (including groups containing ethyleneoxy or propyleneoxy repeating units), aryloxy, acyloxy, acyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, urethane, carboxyl, imido, amino, carbonamido, sulfonamido, ureido, thioureido, sulfamoylamino, semicabazido, thiosemicabazido, groups containing hydrazino, groups containing quaternary ammonio, (alkyl, aryl or heterocyclic)thi
• substituent groups include straight chain, branched or cyclic alkyl (preferably having from 1 to 20 carbon atoms), aralkyl (preferably having from 1 to 20 carbon atoms), alkoxyl (preferably having from 1 to 20 carbon atoms), substituted amino (preferably, substituted amino having from 1 to 20 carbon atoms), acylamino (preferably having from 2 to 30 carbon atoms), sulfonamido (preferably having from 1 to 30 carbon atoms), ureido (preferably having from 1 to 30 carbon atoms), carbamoyl (preferably having from 1 to 30 carbon atoms) and phosphoric acid amido (preferably having 1 to 30 carbon atoms).
• the alkyl group represented by R 2 is preferably an alkyl group having from 1 to 10 carbon atoms, and the aryl group is preferably a monocyclic or bicyclic aryl group, for example, a group containing a benzene ring.
• the heterocyclic group is a 5- or 6-membered ring compound containing at least one of nitrogen, oxygen and sulfur atoms.
• Examples thereof include imidazolyl, pyrazolyl, triazolyl, tetrazolyl, pyridyl, pyridinio, quinolinio and quinolinyl groups. Pyridyl and pyridinio groups are particularly preferred.
• the alkoxyl group is preferably an alkoxyl group having from 1 to 8 carbon atoms, and the aryloxy group is preferably a monocyclic group.
• the amino group is preferably an unsubstituted amino group or an alkyl-, aryl- or heterocyclic- amino group having from 1 to 10 carbon atoms.
• R 2 may be substituted, and preferred substituent groups are the same as those exemplified as the substituent on R 1 .
• G 1 is a -CO-group
• a preferred example is a hydrogen atom, an alkyl group (for example, methyl, trifluoromethyl, difluoromethyl, 2-carboxytetrafluoroethyl, pyridiniomethyl, 3-hydroxypropyl, 3-methanesulfonamidopropyl or phenylsulfonylmethyl), an aralkyl group (for example, o-hydroxybenzyl) or an aryl group (for example, phenyl, 3,5-dichlorophenyl, o-methanesulfonamidophenyl, o-carbamoylphenyl, 4-cyanophenyl or 2-hydroxymethylphenyl).
• a hydrogen atom and an alkyl group are preferred.
• R 2 is preferably an alkyl group (for example, methyl), an aralkyl group (for example, o-hydroxybenzyl), an aryl group (for example, phenyl) or a substituted amino group (for example, dimethylamino).
• R 2 is preferably an alkoxyl group, an aryloxy group or an amino group.
• a substituted amino group for example, 2,2,6,6-tetramethylpiperidine-4-ylamino, propylamino, anilino, o-hydroxyanilino, 5-benzotriazolylamino or N-benzyl-3-pyridinioamino is preferred.
• R 2 may be a group which cleaves the G 1 -R 2 moiety from the residual molecule to induce the cyclization reaction to form a cyclic structure containing atoms of the -G 1 -R 2 moiety, and examples thereof include groups described in JP-A-63-29751.
• a 1 and A 2 are hydrogen atoms, alkyl or arylsulfonyl groups having 20 or less carbon atoms (preferably phenylsulfonyl or phenylsulfonyl substituted so as to give a sum of Hammett substituent constants of -0.5 or more), or acyl groups having 20 or less carbon atoms (preferably, benzoyl or benzoyl substituted so as to give a sum of Hammett substituent constants of -0.5 or more, or straight chain, branched or cyclic, unsubstituted or substituted aliphatic acyl (examples of substituent groups include halogen, ether, sulfonamido, carbonamido, hydroxyl, carboxyl and sulfonic acid)).
• a 1 and A 2 are most preferably hydrogen atoms.
• the substituent groups on R 1 and R 2 of general formula (11) may be further substituted, and preferred examples thereof include the groups exemplified as a substituent group on R 1 .
• the substituent groups may be further substituted in multiple, such as substitution of the substituent group, substitution of the substituent group on the substituent group, substitution of the substituent group on the substituent groups on the substituent groups, etc., and preferred examples thereof also include the groups exemplified as the substituent group on R 1 .
• R 1 or R 2 of general formula (11) may be a group in which a ballast group or a polymer commonly used in an inert photographic additive such as a coupler is incorporated.
• the ballast group is a group having 8 or more carbon atoms which are relatively inactive to photographic characteristics.
• the ballast group can be selected from alkyl, aralkyl, alkoxyl, phenyl, alkylphenyl, phenoxy, alkylphenoxy, etc.
• the polymer include, for example, polymers described in JP-A-1-100530.
• R 1 or R 2 of general formula (11) may be a group in which an adsorbent group for adsorbing a silver halide is incorporated.
• adsorbent groups include groups such as alkylthio, arylthio, thiourea, thioamido, mercapto heterocyclic and triazole groups described in U.S.
• These adsorbent groups to the silver halides may be precursors thereof. Such precursors include groups described in JP-A-2-285344.
• R 1 or R 2 of general formula (11) may contain a plurality of hydrazino groups as substituent groups.
• the compound represented by general formula (11) is an oligomer in terms of hydrazino groups, and specific examples thereof include compounds described in JP-A-64-86134, JP-A-4-16938 and JP-A-5-197091.
• R 1 is particularly preferably a substituted phenyl group, and the phenyl group is preferably substituted by a ballast group, an adsorbent group to a silver halide, a group containing an quaternary ammonio group, a group containing repeating units of ethyleneoxy groups, an alkyl, aryl or heterocyclic thio group, a group dissociatable in an alkaline developer (such as carboxyl, sulfo or acylsulfamoyl), or a hydrazino group which can form an oligomer, via a sulfonamido group, an acylamino group, an ureido group or a carbamoyl group.
• a ballast group such as carboxyl, sulfo or acylsulfamoyl
• R 1 is most preferably a phenyl group substituted by a benzenesulfonamido group, and the benzenesulfonamido group preferably has any of the substituent groups described above as a substituent on the phenyl group.
• G 1 is preferably a -CO- group or a -COCO- group, and particularly preferably a -CO- group. It is particularly preferred that when G 1 is a -CO- group, R 2 is a hydrogen atom, a substituted alkyl group or a substituted aryl group (an electron attractive group or an o-hydroxymethyl group is preferred as a substituent group), and that when G 1 is a -COCO- group, R 2 is a substituted amino group.
• hydrazine derivatives can also be preferably used in the present invention.
• the hydrazine derivatives for use in the present invention can also be synthesized by various methods described in the following patents.
• the hydrazine nucleating agent can be used by dissolving it in an appropriate water-miscible organic solvent, for example, alcohols (such as methanol, ethanol, propanol and fluorinated alcohol), ketones (such as acetone and methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide and methyl cellosolve.
• alcohols such as methanol, ethanol, propanol and fluorinated alcohol
• ketones such as acetone and methyl ethyl ketone
• dimethylformamide dimethyl sulfoxide and methyl cellosolve.
• the hydrazine nucleating agent can also be dissolved using an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate and diethyl phthalate or an auxiliary solvent such as ethyl acetate and cyclohexanone to mechanically prepare emulsified dispersions for use of it.
• an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate and diethyl phthalate or an auxiliary solvent such as ethyl acetate and cyclohexanone to mechanically prepare emulsified dispersions for use of it.
• the hydrazine derivatives can also be used by dispersing the powder thereof in water with a ball mill, a colloid mill or ultrasonic waves.
• the hydrazine nucleating agent may be added to any of the silver halide emulsion layer and other hydrophilic colloidal layers provided on the silver halide emulsion layer side of the support.
• the hydrazine nucleating agent is preferably added to the silver halide emulsion layer or hydrophilic colloidal layers adjacent thereto.
• the amount of the nucleating agent added is preferably 1X10 -6 to 1X10 -2 mol per mol of silver halide, more preferably 1X10 -5 to 5X10 -3 mol, and most preferably 2X10 -5 to 5X10 -3 mol.
• Nucleating accelerators for use in the present invention include amine derivatives, onium salts, disulfide derivatives and hydroxymethyl derivatives. Examples thereof are enumerated below.
• the nucleating accelerator can be used by dissolving them in an appropriate water-miscible organic solvent, for example, alcohols (such as methanol, ethanol, propanol and fluorinated alcohol), ketones (such as acetone and methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide and methyl cellosolve.
• alcohols such as methanol, ethanol, propanol and fluorinated alcohol
• ketones such as acetone and methyl ethyl ketone
• dimethylformamide dimethyl sulfoxide and methyl cellosolve.
• the nucleating accelerator can also be dissolved using an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate and diethyl phthalate or an auxiliary solvent such as ethyl acetate and cyclohexanone to mechanically prepare emulsified dispersions for use of it.
• the nucleating accelerator can also be used by dispersing the powder thereof in water with a ball mill, a colloid mill or ultrasonic waves.
• the nucleating accelerator may be added to any of the silver halide emulsion layer and other hydrophilic colloidal layers on the silver halide emulsion layer side of the support.
• the nucleating accelerator is preferably added to the silver halide emulsion layer or hydrophilic colloidal layers adjacent thereto.
• the amount of the nucleating accelerator added is preferably 1X10 -6 to 2X10 -2 mol per mol of silver halide, more preferably 1X10 -5 to 2X10 -2 mol, and most preferably 2X10 -5 to 1X10 -2 mol.
• the ascorbic acid derivative for use in the present invention as a developing agent is preferably compounds represented by the following general formula (12): wherein R 1 and R 2 each represents a hydroxyl group, an amino group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkoxycarbonylamino group, a mercapto group or an alkylthio group; and X comprises a carbon atom, an oxygen atom or a nitrogen atom, and forms a 5- or 6-membered ring together with the two vinyl carbon atoms at which R 1 and R 2 are substituted and the carbonyl carbon atom in general formula (12).
• General formula (12) is described in detail below.
• R 1 and R 2 each represents a hydroxyl group, an amino group (including amino groups having an alkyl group with 1 to 10 carbon atoms as a substituent group, for example, methyl, ethyl, n-butyl or hydroxyethyl), an acylamino group (such as acetylamino or benzoylamino), an alkylsulfonylamino group (such as methanesulfonylamino), an arylsulfonylamino group (such as benzenesulfonylamino or p-toluenesulfonylamino), an alkoxycarbonylamino group (such as methoxycarbonylamino), a mercapto group or an alkylthio group (such as methylthio or ethylthio).
• an amino group including amino groups having an alkyl group with 1 to 10 carbon atoms as a substituent group, for example, methyl
• R 1 and R 2 include hydroxyl, amino, alkylsulfonylamino and arylsulfonylamino groups.
• X comprises a carbon atom, an oxygen atom or a nitrogen atom, and forms a 5- or 6-membered ring together with the two vinyl carbon atoms at which R 1 and R 2 are substituted and the carbonyl carbon atom.
• the 5- or 6-membered ring may comprises a saturated or unsaturated condensed ring.
• the 5- and 6-membered ring include dihydrofuranone, dihydropyrone, pyranone, cyclopentenone, cyclohexenone, pyrrolinone, pyrazolinone, pyridone, azacyclohexenone and uracil rings.
• Preferred examples thereof include dihydrofuranone, cyclopentenone, cyclohexenone, pyrazolinone, azacyclohexenone and uracil rings.
• the endiol type, enaminol type, the endiamin type, the thiol-enol type and the enamin-thiol type are generally known. Examples of these compounds are described in U.S. Patent 2,688,549 and JP-A-62-237443. Synthesis methods of these ascorbic acid derivatives are also well known, and are described, for example, in Tsugio Nomura and Hirohisa Ohmura, Chemistry of Reductons , Uchida Rohkakuho Shinsha (1969).
• the ascorbic acid derivatives for use in the present invention can also be used in the form of alkali metal salts such as lithium salts, sodium salts and potassium salts.
• p-Aminophenol developing agents for use in the present invention include N-methyl-p-aminophenol, p-aminophenol, N-( ⁇ -hydroxyphenyl)-p-aminophenol and N-(4-hydroxyphenyl)-glycine, and N-methyl-p-aminophenol is preferred among others.
• 3-pyrazolidone or derivatives thereof are generally used as auxiliary developing agents, the use of 3-pyrazolidone or the derivatives thereof is unfavorable in the present invention.
• 3-Pyrazolidone and the derivatives thereof inhibit nucleating development induced by hydrazine compounds to cause reductions in sensitivity and contrast. It is therefore preferred not to use 3-pyrazolidone and the derivatives thereof.
• the ascorbic acid derivative developing agent is preferably used in an amount of 0.01 mol/liter to 0.5 mol/liter, and more preferably in an amount of 0.05 mol/liter to 0.3 mol/liter.
• the developer for use in processing the photographic materials in the present invention can contain commonly used additives (for example, developing agents, alkali agents, pH buffers, preservatives and chelating agents). Specific examples thereof are shown below, but the present invention is not limited thereto.
• the buffer for use in the developer for developing the photographic materials in the present invention includes carbonates, boric acid described in JP-A-62-286259, saccharides (for example, saccharose) described in JP-A-60-93433, oximes (for example, acetoxime), phenols (for example, 5-sulfosalicylic acid) and tertiary phosphates (for example, sodium salts and potassium salts), and the carbonates and boric acid are preferably used.
• the buffers, particularly carbonates are preferably used in an amount of 0.5 mol/liter or more, and particularly preferably in an amount of from 0.5 to 1.5 mol/liter.
• the preservative for use in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite and sodium formaldehydebisulfite.
• the concentration of the sulfite is preferably from 0.01 mol/liter to 0.05 mol/liter. If the concentration of the sulfite is too high, the amount of silver eluted from the photographic material to the developer increases to unfavorably cause silver stain.
• the pH of developing replenisher is at least 0.2 higher than that of the starting developing solution.
• the ascorbic acid as the developing agent releases an acid by processing fatigue to largely lower the pH of the developer.
• too high a pH deteriorates the resistance to air oxidation of the replenisher itself.
• the pH of the developing replenisher is preferably 9.0 to 10.5, and the pH of the starting developing solution is preferably 8.8 to 10.3.
• the difference in pH between the developing replenisher and the starting developing solution is preferably established to 0.2 to 1.0, and more preferably to 0.3 to 0.7.
• the replenishment rate of the developing replenisher 15 preferably not more than 300 ml per m 2 of the photographic material, and more preferably from 30 ml/m 2 to 250 ml/m 2 .
• the developing replenisher may have the same composition as that of the starting developing solution, except for the pH, or may have a composition different therefrom.
• the starting developing solution means a so-called fresh solution (a developer placed in a development tank of an automatic processor at first and not used in photographic processing).
• the developing replenisher and the starting developing solution for use in the present invention are each substantially free from a dihydroxybenzene compound, and each contains the ascorbic acid and/or the derivative thereof as a developing agent, and further contains the aminophenol derivative as an auxiliary developing agent exhibiting a superadditive property and at least 0.5 mol/liter of a carbonate as a buffer.
• the phrase "substantially free from” used herein means that even if the solutions contain a dihydroxybenzene compound, the content thereof is too small to contribute to the development.
• the replenisher and the starting solution may contain a dihydroxybenzene compound in an amount such that it does not affect the development. Such an amount is generally about not more than 0.02 mol/liter.
• Additives for use in addition to the above include development inhibitors such as sodium bromide and potassium bromide; organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol and dimethylformamide; and development accelerators such as alkanolamines (e.g., diethanolamine and triethanolamine) and imidazole or derivatives thereof.
• development inhibitors such as sodium bromide and potassium bromide
• organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol and dimethylformamide
• development accelerators such as alkanolamines (e.g., diethanolamine and triethanolamine) and imidazole or derivatives thereof.
• Heterocyclic mercapto compounds such as sodium 3-(5-mercaptotetrazole-1-yl)benzenesulfonate and 1-phenyl-5-mercaptotetrazole
• JP-A-62-212651 can also be added as uneven physical development inhibitors.
• mercapto compounds, indazole compounds, benzotriazole compounds and benzoimidazole compounds may be contained as antifoggants or black pepper inhibitors.
• examples thereof include 5-nitroindazole, 5-p-nitrobenzoyl-aminoindazole, 1-methyl-5-nitroindazole, 6-nitroindazole, 3-methyl-5-nitroindazole, 5-nitrobenzindazole, 2-isopropyl-5-nitrobenzimidazole, 5-nitrobenzotriazole, sodium 4-((2-mercapto-1,3,4-thiadiazole-2-yl)thio)butanesulfonate, 5-amino-1,3,4-thiadiazole-2-thiol, methylbenzotriazole, 5-methylbenzotriazole and 2-mercaptobenzotriazole.
• the amount of these additives is usually from 0.01 to 10 mmol, and more preferably from 0.1 to 2 mmol per liter of the developer.
• Sodium tetrapolyphosphate and sodium hexametaphosphate can be used as the inorganic chelating agents.
• organic carboxylic acids, aminopoly-carboxylic acids, organic phosphonic acids, aminophosphonic acids and organic phosphonocarboxylic acids can be mainly used as the organic chelating agents.
• the organic carboxylic acids include, for example, acrylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, gluconic acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, maleic acid, itaconic acid, malic acid, citric acid and tartaric acid.
• the aminopolycarboxylic acids include, for example, aspartic acid diacetic acid, iminodiacetic acid, nitrilotriacetic acid, nitrilotripropionic acid, ethylenediaminemonohydroxyethyltriacetic acid, ethylenediaminetetraacetic acid, glycolethertetraacetic acid, 1,2-diaminopropanetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, 1,3-diamino-2-propanoltetraacetic acid, glycoletherdiaminetetraacetic acid and compounds described in JP-A-52-25632, JP-A-55-67747, JP-A-57-102624 and JP-B-53-40900.
• organic phosphonic acids examples include hydroxyalkylidenediphosphonic acids described in U.S. Patents 3,214,454 and 3,794,591 and West German Patent Publication (OLS) 2,227,396, and compounds described in Research Disclosure , 181 , Item 18170 (May, 1979).
• aminophosphonic acids include, for example, compounds described in Research Disclosure , 18170 described above, JP-A-57-208554, JP-A-54-61125, JP-A-55-29883 and JP-A-56-97347, as well as aminotris(methylenephosphonic acid), ethylenediaminetetramethylenephosphonic acid and aminotri-methylenephosphonic acid.
• organic phosphonocarboxylic acids examples include compounds described in JP-A-52-102726, JP-A-53-42730, JP-A-54-121127, JP-A-55-4024, JP-A-55-4025, JP-A-55-126241, JP-A-55-65955, JP-A-55-65956 and Research Disclosure , 18170 described above.
• organic and/or inorganic chelating agents are not limited to the above-described agents, and may be used in the form of alkali metal salts or ammonium salts.
• the amount of these chelating agents added is preferably from 1X10 -4 to 1X10 -1 mol per liter of developer, and more preferably from 1X10 -3 to 1X10 -2 mol per liter of the developer.
• fixing agents of fixing processing agents in the present invention ammonium thiosulfate, sodium thiosulfate and ammonium sodium thiosulfate can be used.
• the amount of the fixing agent used can be appropriately changed, but it is generally from about 0.7 to about 3.0 mol/liter.
• the fixing solution for use in the present invention may contain water-soluble aluminum salts or water-soluble chromium salts acting as hardening agents, and water-soluble aluminum salts are preferred.
• water-soluble aluminum salts include aluminum chloride, aluminum sulfate, potassium alum, ammonium aluminum sulfate, aluminum nitrate and aluminum lactate. It is preferred that these are contained in an amount of 0.01 to 0.15 mol/liter in terms of the aluminum ion concentration in working solutions.
• the fixing solution When the fixing solution is preserved as a concentrated solution or solid agents, they may be composed of a plurality of parts with separating from the hardeners and the like as other parts, or may be composed of one part containing all components.
• the fixing processing agents can contain preservatives (for example, 0.015 mol/liter or more, preferably from 0.02 mol/liter to 0.3 mol/liter of sulfites, bisulfites or metabisulfites), pH buffers (for example, from 0.1 mol/liter to 1 mol/liter, preferably from 0.2 mol/liter to 0.7 mol/liter of acetic acid, sodium acetate, sodium carbonate, sodium hydrogencarbonate, phosphoric acid, succinic acid or adipic acid) and compounds having aluminum-stabilizing ability or water-softening ability (for example, from 0.001 mol/liter to 0.5 mol/liter, preferably from 0.005 mol/liter to 0.3 mol/liter of gluconic acid, iminodiacetic acid, 5-sulfosalicylic acid, glucoheptanoic acid, malic acid, tartaric acid, citric acid, oxalic acid, maleic acid, glycolic acid, benzoic acid, salicylic
• the fixing processing agent can contain compounds described in JP-A-62-78551, pH regulators (for example, sodium hydroxide, ammonium and sulfuric acid), surfactants, wetting agents and fixing accelerators.
• the surfactants include, for example, anionic surfactants such as sulfates and sulfonates, polyethylene surfactants and amphoteric surfactants as described in JP-A-57-6840, and known antifoaming agents can also be used.
• the wetting agents include alkanolamines and alkylene glycols.
• the fixing accelerators include alkyl- and allyl-substituted thiosulfonic acids and salts thereof as described in JP-A-6-308681, thiourea derivatives described in JP-B-45-35754, JP-B-58-122535 and JP-B-58-122536, alcohols having a triple bond in its molecule, thioether compounds described in U.S. Patent 4,126,459, mercapto compounds described in JP-A-64-4739, JP-A-1-4739, JP-A-1-159645 and JP-A-3-101728, mesoionic compounds described in JP-A-4-170539, and thiocyanates.
• the pH of the fixing solution for use in the present invention is 4.0 or more, and preferably from 4.5 to 6.0.
• the replenishment rate of the fixing solution is not more than 500 ml per m 2 of the photographic material, preferably not more than 390 ml/m 2 , and more preferably from 30 ml/m 2 to 320 ml/m 2 .
• the replenisher may have the same composition and/or concentration as that of the starting solution, or may have a composition and/or a concentration different therefrom.
• the fixing solution can be regenerated by known regeneration methods of a fixing solution such as electrolytic silver recovery to use it.
• Regeneration devices include Reclaim R-60 manufactured by Fuji Hunt Electronics Technology Co. Ltd.
• the developing processing agent and the fixing processing agent for use in the present invention are preserved in the liquid form, they are preferably stored in wrapping up in packaging materials having a low oxygen permeability as described, for example, in JP-A-61-73147. Further, when these solutions are supplied as concentrated solutions, the concentrated solutions are diluted with water to give a predetermined concentration at the time of use, for example, at a rate of from 0.2 to 3 parts of water per part of the concentrated solution.
• the developing processing agent and the fixing processing agent for use in the present invention provide results similar to those when used in the liquid form, also when used in the solid form, and solid processing agents are described below.
• the solid processing agents for use in the present invention can be used in known forms (such as powdery, granular, massive, tablet, compactor, briquette, tabular, breaked, rod-like and paste-like forms).
• the components may be coated with water-soluble coating agents or coating films, or may be formed in a plurality of layers to separate the components which react with each other, or these methods may be used in combination.
• polyvinylpyrrolidone polyethylene glycol, polystyrenesulfonic acid and vinyl compounds are preferred.
• gelatin pectin, polyacrylic acid, polyvinyl alcohol, vinyl acetate copolymers, polyethylene oxide, sodium carboxymethyl cellulose, hydroxypropyl cellulose, methyl cellulose, ethyl cellulose, alginic acid, chitaric acid gum, gum arabic, tragacanth gum, carrageenan, methyl vinyl ether, maleic anhydride copolymers, polyoxyethylene alkyl ethers such as polyoxyethylene stearyl ether and polyoxyethylene ethyl ether, polyoxyethylene alkylphenol ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether, and water-soluble binders described in EP-A-469877 are used alone or as a combination of two or more thereof. These can also be used as granulating
• a component which does not react even in contact may be put between components which react with each other, to thereby form a plural-layered product, which may be processed to the tablet or briquette form, or components of known forms may be formed to similar constitution, which may be wrapped.
• the apparent density of the solid processing agent is preferably from 0.5 to 6.0 g/cm 3 . In particular, it is preferably from 1.0 to 5.0 g/cm 3 for tablet forms, and from 0.5 to 1.5 g/cm 3 for the granules.
• any of known methods can be used.
• methods described in JP-A-61-259921, JP-A-4-16841 and JP-A-4-78848 can be used as packaging methods.
• methods described in JP-A-4-85533, JP-A-4-85534, JP-A-4-85535, JP-A-5-134362, JP-A-5-197070, JP-A-5-204098, JP-A-5-224361, JP-A-6-138604 and JP-A-6-138605 can be used as solidifying methods. More specifically, rolling granulation, extrusion granulation, compression granulation, pulverization granulation, stirring granulation, spray drying, dissolution coagulation, briquetting and roller compacting can be used.
• the grain size and the form of granulated products suitable for the present invention vary depending on desired characteristics. However, considering the solubility generally desired for photographic processing agents and the amount of residual powders in packaging materials after solution preparation, or considering the resistance to destruction of the granulated products by vibration in transferring, the grain size (converted to the spherical size) of the granular products is from about 0.5 to about 50 mm, and preferably from about 1 to about 15 mm, and the form thereof is cylindrical, spherical, cubic or rectangular parallelepiped form, and preferably spherical or cylindrical.
• Products processed by roller compacting may be pulverized, and further filtered to obtain a size of from about 2 mm to about 1 cm.
• the grain size and the form similarly vary depending on desired characteristics, the grain size is preferably about 2 mm to about 5 cm, and the form is cylindrical, spherical, cubic or rectangular parallelepiped form, and preferably spherical or cylindrical.
• tabular products decreased in thickness, products further decreased in thickness of central portions thereof and hollow doughnut-shaped are also useful.
• the size or the thickness may be increased, and can be arbitrarily adjusted.
• the surface conditions (such as smoothness and porousness) may be changed, furthermore, in order to give different solubilities to a plurality of products or match the solubility of materials different in solubility, it is also possible to use a plurality of forms.
• a multilayer granulated product may also be used in which a surface thereof is different from the inside thereof in composition.
• packaging materials for the solid processing agents materials having low oxygen permeability and low moisture permeability are preferred, and those in known forms such as bag-like, cylindrical and box-like forms can be used for the packaging materials.
• Collapsible forms as disclosed in JP-A-6-242585, JP-A-6-242586, JP-A-6-242587, JP-A-6-242588, JP-A-6-247432, JP-A-6-247448, JP-A-7-5664, JP-A-7-5666, JP-A-7-5667, JP-A-7-5668 and JP-A-7-5669 are also preferred to decrease the space for storing waste packaging materials.
• These packaging materials may be provided with screw caps, pull tops or aluminum seals at outlets for the processing agents, or heat sealed. However, other known means may be used, without limitation thereto. It is preferred in respect to environmental protection to recycle or reuse the waste packaging materials.
• the package may be either manually opened to supply the processing agent, or automatically opened to automatically supply the processing agent with a dissolving device or an automatic processor having an opening mechanism.
• the latter is preferred from the viewpoint of working environment.
• washing and stabilization processing a solution used therefor is referred to as water or washing water.
• Water used for washing may be tap water, ion-exchanged water, distilled water or stabilized water.
• the replenishment rate thereof is generally from about 8 liters to about 17 liters per m 2 of the photographic material, but washing can also be conducted at a replenishment rate of less than the above range. In particular, washing at a replenishment rate of 3 liters or less (including 0, namely pool washing) not only makes water-saving processing possible, but also can make piping for installation of an automatic processor unnecessary.
• oxidizing agents for example, ozone, hydrogen peroxide, sodium hypochlorite, active halogen, chlorine dioxide and sodium carbonate peroxyhydrate
• filtration through filters may be combined with each other.
• a multi-stage countercurrent system for example, two-stage, three-stage and the like
• the replenishment rate of washing water is preferably from 50 to 200 ml per m 2 of the photographic material. This effect is also similarly obtained by an independent multi-stage system (a method for replenishing a fresh solution to multi-stage washing tanks, separately, without use of countercurrent replenishment).
• water scale prevention means may be applied to a fixing stage in the method of the present invention.
• known means can be used, and there is no particular limitation thereon. Examples thereof include methods of adding antifungal agents (so-called water scale inhibitors), methods of passing electric currents, methods of irradiating ultraviolet rays, infrared rays or far infrared rays, methods of applying magnetic fields, methods of treating with ultrasonic waves, methods of applying heat and methods of making tanks empty at the time of nonuse.
• These water scale prevention means may be applied according to the processing of the photographic materials, or at certain intervals, regardless of the conditions of use, or only for periods in which the processing is not conducted, for example, at night. Further, washing water previously subjected to the water scale prevention means may be replenished. It is also preferred for prevention of generation of resistant bacteria to apply different water scale prevention means for every definite period.
• antifungal agents there is no particular limitation on the antifungal agents, and known ones can be used.
• examples thereof include chelating agents such as glutaraldehyde and aminopolycarboxylic acid, cationic surfactants and mercaptopyridine oxide (for example, 2-mercaptopyridine-N-oxide), as well as the above-described oxidizing agents. They may be used alone or in combination of two or more thereof.
• An overflowed solution from the washing stage can also be partly or wholly mixed with a processing solution having fixing ability to use the mixed solution, as described in JP-A-60-235133. It is also preferred from the view point of natural environmental protection to reduce the concentration of silver contained in drainage by draining after decreases in biological oxygen demand (BOD), chemical oxygen demand (COD) and iodine consumption by biological treatments (for example, treatments with filters in which sulfur-oxidizing bacteria, activated sludge or microorganisms are carried on porous carriers such as activated carbon and ceramics) or by oxidation treatments by electric current passing or with oxidizing agents, or by precipitating silver by use of filters using polymers having affinity for silver or addition of compounds forming slightly soluble silver complexes of trimercaptotriazine, etc.
• BOD biological oxygen demand
• COD chemical oxygen demand
• iodine consumption by biological treatments (for example, treatments with filters in which sulfur-oxidizing bacteria, activated sludge or microorganisms are carried on porous carriers such
• washing processing may be followed by stabilization processing.
• baths containing compounds described in JP-A-2-201357, JP-A-2-132435, JP-A-1-102553 and JP-A-46-44446 may be used as final baths for the photographic materials.
• Ammonium compounds, compounds of metals such as Bi and Al, fluorescent whitening agents, various chelating agents, membrane pH regulators, hardening agents, disinfectants, antifungal agents, alkanolamines or surfactants can also be added to these stabilizing baths, if necessary.
• Additives such as the antifungal agents added to the washing and stabilizing baths and stabilizing agents can also be used as solid agents similarly with the above-described developing and fixing processing agents.
• Waste liquids of the developer, the fixing solution, the washing water and the stabilizing solution for use in the present invention are preferably burned to dispose them. It is also possible to concentrate or solidify these waste liquids with a concentrating device as described in JP-B-7-83867 and U.S. Patent 5,439,560, followed by disposition.
• roller transfer type automatic processors are described in U.S. Patents 3,025,779 and 3,545,971, and briefly referred to as roller transfer type automatic processors in this specification.
• This automatic processor comprises the four stages of development, fixing, washing and drying. It is most preferred that the methods of the present invention also follow these four stages, although not excluding another stage (for example, a stop stage). Further, a rinsing bath may be provided between development and fixing, and/or between fixing and washing.
• the development processing is preferably conducted for from 25 to 160 seconds at dry to dry.
• the developing and fixing time is 40 seconds or less, and preferably from 6 to 35 seconds, and the temperature of each solution is preferably from 25 to 50°C, and more preferably from 30 to 40°C.
• the temperature and the time of washing are preferably from 0 to 50°C and 40 seconds or less, respectively.
• washing water may be squeezed off from the photographic material which have been developed, fixed and washed, namely, such a material may be passed between squeeze rolls, followed by drying.
• the drying is carried out at from about 40 to about 100°C, and the drying time can be appropriately varied according to the environmental conditions. Any of known drying methods can be used, and there is no particular limitation thereon. Examples thereof include hot air drying, heat roller drying described in JP-A-4-15534, JP-A-5-2256 and JP-A-5-289294, and drying by far infrared rays, and the plural methods may be used in combination.
• the silver halide emulsion for use in the photographic material of the present invention can contain any silver halides used in ordinary silver halide emulsions, such as silver bromide, silver iodobromide, silver chloride, silver chlorobromide and silver chloroiodobromide.
• Silver chlorobromide containing 60 mol% or more of silver chloride is preferred for a negative type silver halide emulsion
• silver chlorobromide, silver bromide and silver iodobromide containing 60 mol% or more of silver bromide are preferred for a positive type silver halide emulsion.
• the silver halide grains may be obtained by any of the acidic method, the neutral method and the ammonia method.
• the silver halide grain may be either a grain having uniform silver halide composition distribution therein or a core/shell grain in which the inside of the grain is different from a surface of the grain in silver halide composition.
• the silver halide grain may be either a grain in which a latent image is mainly formed on a surface of the grain or a grain in which a latent image is mainly formed in the inside of the grain. Further, the grain may be a grain whose surface is previously fogged.
• the form of the silver halide grain according to the present invention may be any. One preferred example thereof is a cube having a ⁇ 100 ⁇ face as a crystal surface.
• grains having octahedral, tetradecahedral or dodecahedral form produced by methods described U.S. Patents 4,183,756 and 4,225,666, JP-A-55-26589, JP-B-55-42737 and J. Photogr. Sci. , 21-39 (1973) can also be used. Furthermore, grains having twin planes may be used.
• the silver halide grain for use in the present invention may be either grains having a single form, or mixed grains comprising those having various forms. In the present invention, monodisperse emulsions are preferred.
• Monodisperse silver halide grains in the monodisperse emulsions are preferably those in which the weight of silver halides contained within the grain size range of a mean grain size ⁇ ⁇ 10% accounts for 60% or more of the total weight of silver halide grains.
• halogen composition of the silver halide emulsion for use in the present invention.
• silver chloride, silver chlorobromide and silver chloroiodobromide having a silver halide content of 50 mol% or more are preferred.
• the content of silver iodide is preferably less than 5 mol%, and more preferably less than 2 mol%.
• photographic materials suitable for high illumination exposure such as scanner exposure and photographic materials for line camera work generally contain a rhodium compound in order to achieve high contrast and low fog.
• water-soluble rhodium compounds can be used.
• examples thereof include rhodium (III) halide compounds or rhodium complex salts having a halogen, an amine, oxalato or the like as a ligand, for example, hexachlororhodium (III) complex salts, hexabromorhodium (III) complex salts, hexaaminerhodium (III) complex salts and trioxalatorhodium (III) complex salts.
• rhodium compounds are dissolved in water or an appropriate solvent to use them.
• a method generally frequently used that is, the method of adding an aqueous solution of a hydrogen halide (for example, hydrochloric acid, hydrobromic acid or hydrofluoric acid) or an alkali halide (for example, KCl, NaCl, KBr or NaBr) can be used.
• a hydrogen halide for example, hydrochloric acid, hydrobromic acid or hydrofluoric acid
• an alkali halide for example, KCl, NaCl, KBr or NaBr
• the amount added is generally from 1X10 -8 to 5X10 -6 mol per mol of silver contained in the silver halide emulsion, and preferably from 5X10 -8 to 1X10 -6 mol.
• Addition of these compounds can be appropriately conducted in preparing the silver halide emulsion grains and in each stage prior to coating of the emulsions.
• the compounds are preferably added in forming the emulsions to incorporate them into the silver halide grains.
• the photographic emulsions for use in the present invention can be prepared by use of the methods described in P. Glafkides, Chimie et Physique Photographique (Paul Montel, 1967), G. F. Duffin, Photographic Emulsion Chemistry (The Focal Press, 1966) and V. L. Zelikman et al., Making and Coating Photographic Emulsion (The Focal Press, 1964).
• a soluble silver salt and a soluble halogen salt may be reacted with each other by using any of the single jet process, the double jet process and a combination thereof.
• a process in which grains are formed in the presence of excess silver ions can also be used.
• As a type of double jet process there can also be used a process for maintaining the pAg in a liquid phase constant, in which a silver halide is formed, namely the so-called controlled double jet process.
• so-called solvents for silver halides such as ammonium, thioether and tetra-substituted thiourea are used to form grains.
• thiourea compounds More preferably, tetra-substituted thiourea compounds are used, which are described in JP-A-53-82408 and JP-A-55-77737.
• Preferred examples of the thiourea compounds are tetramethylthiourea and 1,3-dimethyl-2-imidazolidinethione.
• silver halide emulsions having a regular crystal form and a narrow grain size distribution can be readily prepared. These processes are useful means for preparing the silver halide emulsions for use in the present invention.
• silver halide grains for use in the present invention there is no particular limitation on the form of silver halide grains for use in the present invention, and tabular silver halide grains having a high aspect ratio described in Research Disclosure , 22534 (January, 1983), as well as cubic, octahedral and spherical grains, can be used.
• grains are allowed to grow rapidly within the range not exceeding the critical degree of saturation by the method of changing the addition rate of silver nitrate and alkali halides depending on the growth speed of grains as described in British Patent 1,535,016, JP-B-48-36890 and JP-B-52-16364, and the method of changing the concentration of aqueous solutions as described in British Patent 4,242,445 and JP-A-55-158124.
• the emulsion for use in the present invention is preferably a monodisperse emulsion, and the coefficient of variation thereof is 20% or less, and particularly preferably 15% or less.
• the mean grain size of the grains contained in the monodisperse silver halide emulsion is 0.5 ⁇ m or less, and particularly preferably from 0.1 ⁇ m to 0.4 ⁇ m.
• the silver halide emulsion for use in the present invention is preferably subjected to chemical sensitization.
• chemical sensitization methods known methods such as sulfur sensitization, selenium sensitization, tellurium sensitization and noble metal sensitization can be used alone or in combination. When they are used in combination, for example, sulfur sensitization and gold sensitization; sulfur sensitization, selenium sensitization and gold sensitization; and sulfur sensitization, tellurium sensitization and gold sensitization are preferred.
• the sulfur sensitization for use in the present invention is usually conducted by adding a sulfur sensitizer and stirring an emulsion at a high temperature of 40°C or more for a definite period of time.
• a sulfur sensitizer known compounds can be used. Examples thereof include various sulfur compounds such as thiosulfates, thiourea compounds, thiazole compounds and rhodanine compounds, as well as sulfur compounds contained in gelatin.
• Preferred sulfur compounds are thiosulfates and thiourea compounds.
• the amount of the sulfur sensitizers added varies depending on various conditions such as the pH and the temperature in chemical ripening and the size of silver halide grains, it is preferably from 10 -7 to 10 -2 mol per mol of silver halide, and more preferably from 10 -5 to 10 -3 mol.
• sulfur sensitizers various sulfur compounds such as thiosulfates, thiourea compounds, thiazole compounds and rhodanine compounds, as well as sulfur compounds contained in gelatin, can be used.
• Preferred sulfur compounds are thiosulfates and thiourea compounds, and the pAg in the chemical sensitization is preferably 8.3 or less, and more preferably within the range of from 7.3 to 8.0.
• selenium sensitizers for use in the present invention known selenium compounds can be used. That is, the selenium sensitization is usually conducted by adding an unstable type and/or non-unstable type selenium compound and stirring an emulsion at a high temperature of 40°C or more, for a definite period of time.
• the unstable type selenium compounds compounds described in JP-B-44-15748, JP-B-43-13489, JP-A-4-109240 and JP-A-4-324855 can be used.
• compounds represented by general formulas (VIII) and (IX) in JP-A-4-324855 are preferably used.
• Tellurium sensitizers for use in the present invention is a compound which produces silver telluride presumed to be a sensitizing nucleus in the surface or the inside of a silver halide grain.
• the forming rate of silver telluride in the silver halide emulsion can be tested by the method described in JP-A-5-313284.
• the amount of the selenium and tellurium sensitizers for use in the present invention varies depending on silver halide grains used, chemical ripening conditions, etc., it is generally from 10 -8 to 10 -2 mol per mol of silver halide, and preferably about from 10 -7 to 10 -3 mol.
• the pH is generally from 5 to 8
• the pAg is generally from 6 to 11 and preferably from 7 to 10
• the temperature is generally from 40 to 95°C and preferably from 45 to 85°C.
• Noble metal sensitizers for use in the present invention include gold, platinum, palladium and iridium, and particularly, gold sensitization is preferred of these.
• gold sensitizers for use in the present invention include chloroauric acid, potassium chloroaurate, potassium aurithiocyanate and gold sulfide. They can be used in an amount of about 10 -7 to 10 -2 mol per mol of silver halide.
• cadmium salts, sulfites, lead salts and thallium salts may be allowed to coexist with the silver halide emulsion for use in the present invention.
• the reduction sensitization can be used.
• reduction sensitizers stannous salts, amines, formamidinesulfinic acid and silane compounds can be used.
• Thiosulfonic acid compounds may be added to the silver halide emulsion for use in the present invention by the method shown in EP-A-293,917.
• the silver halide emulsion in the photographic material for use in the present invention may be used alone or in combination (for example, emulsions different in mean grain size, emulsions different in halogen composition, emulsions different in crystal habit, and emulsions different in the conditions of chemical sensitization).
• silver halide emulsions particularly suitable for photographic materials for dot to dot work comprise silver halides containing 90 mol% or more, more preferably 95 mol% or more, of silver chloride, and silver chlorobromide or silver chloroiodobromide containing 0 to 10 mol% of silver bromide.
• An increase in the proportion of silver bromide or silver iodide unfavorably deteriorates safelight safety in an illuminated room or decreases ⁇ .
• the silver halide emulsion for use in the photographic material for dot to dot work in the present invention contains a complex of a transition metal.
• the transition metal includes Rh, Ru, Re, Os, Ir and Cr.
• the ligand thereof includes nitrosyl and thionitrosyl ligands, halide ligands (fluorides, chlorides, bromides and iodides), cyanide ligands, cyanate ligands, thiocyanate ligands, selenocyanate ligands, tellurocyanate ligands, azido ligands and aquo ligands.
• halide ligands fluorides, chlorides, bromides and iodides
• cyanide ligands fluorides, chlorides, bromides and iodides
• cyanide ligands fluorides, chlorides, bromides and iodides
• cyanide ligands fluorides, chlorides, bromides and iodides
• cyanide ligands fluorides, chlorides, bromides and iodides
• cyanide ligands fluorides, chlorides, bro
• rhodium atoms when rhodium atoms are introduced, they are added as metal salts of any form such as single salts or complex salts in preparing the grains.
• the rhodium salts include rhodium monochloride, rhodium dichloride, rhodium trichloride and ammonium hexachlororhodate, and preferably include water-soluble halogen complex compounds of trivalent rhodium, for example, hexachlororhodic (III) acid or salts thereof (such as ammonium salts, sodium salts and potassium salts).
• hexachlororhodic (III) acid or salts thereof such as ammonium salts, sodium salts and potassium salts.
• These water-soluble rhodium salts are added in an amount ranging from 1.0X10 -6 mol to 1.0X10 -3 mol per mol of silver halide, preferably in an amount of from 1.0X10 -5 mol to 1.0X10 -3 , and particularly preferably in an amount of from 5.0X10 -5 mol to 5.0X10 -4 mol.
• spectral sensitizing dyes for use in the present invention.
• the amount of the sensitizing dyes added varies depending on the form and the size of silver halide grains, they are used in an amount ranging from 4X10 -6 to 8X10 -3 mol per mol of silver halide.
• the amount added is preferably within the range of from 2X10 -7 to 3.5X10 -6 mol per m 2 of surface area of silver halide grain, and more preferably within the range of from 6.5X10 -7 to 2.0X10 -6 mol.
• the light-sensitive silver halide emulsion for use in the present invention may be spectrally sensitized to blue, green, red or infrared light having relatively long wavelengths by use of sensitizing dyes.
• the sensitizing dyes which can be used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, styryl dyes, hemicyanine dyes, oxonol dyes and hemioxonol dyes.
• sensitizing dyes having the spectral sensitivity suitable for spectral characteristics of various scanner light sources can be advantageously selected.
• sensitizing dyes are advantageously selected:
• sensitizing dyes may be used alone or in combination. Combinations of the sensitizing dyes are often used particularly for supersensitization.
• the emulsion may contain a dye having no spectral sensitizing function themselves, or substances which do not substantially absorb visible light and exhibit supersensitization, together with the sensitizing dye.
• the sensitizing dye the combination of the dyes showing supersensitization, and the substances exhibiting supersensitization are described in Research Disclosure , 176 , 17643 IV-J, page 23 (December, 1978).
• S1-1 to S1-13 described in JP-A-8-211571 are preferably used.
• sensitizing dyes represented by general formula (I) described in JP-A-6-75322, page 7, column 11, line 42 to page 8, the last line are particularly preferred.
• compounds I-1 to I-35 described therein are preferred.
• compounds described in general formula (I) of JP-A-6-75322 and I-1 to I-34 of general formula (I) of JP-A-7-287338 are both preferably used.
• LED light sources and the infrared semiconductor lasers it is particularly preferred to use dyes of S3-1 to S3-8 described in JP-A-8-211571.
• dyes of S4-1 to S4-9 described in JP-A-8-211571 are preferably used in addition to these.
• sensitizing dyes of general formula (IV) described in JP-A-6-313937 are preferred, and specifically, IV-1 to IV-20 described therein are preferably used.
• dyes of general formulas (III) and (IV) described in JP-A-4-19647 are preferred, and specifically, III-1 to III-20 and IV-1 to IV-11 described therein are preferably used.
• the compounds which can be added include many compounds known as antifogging agents or stabilizers such as azoles, for example, benzothiazolium salts, nitroindazole compounds, chlorobenzimidazole compounds, bromobenzimidazole compounds, mercaptotetrazole compounds, mercaptothiazole compounds, mercaptobenzothiazole compounds, mercaptothiadiazole compounds, aminotriazole compounds, benzothiazole compounds and nitrobenzotriazole compounds; mercaptotriazine compounds; thioketo compounds such as oxazolinethione; azaindene compounds such as triazaindene compounds, tetraazaindene compounds (particularly, 4-hydroxy-substituted (1,3,3a,7)tetraazainden
• benzotriazole compounds for example, 5-methylbenzotriazole
• nitroindazole compounds for example, 5-nitroindazole
• these compounds may be added to processing solutions.
• compounds releasing inhibitors during development described in JP-A-62-30243 can be added as stabilizers or for preventing black peppers.
• polymer latexes are added to the silver halide emulsion layer or a backing layer to improve dimension stability. These techniques are described, for example, in JP-B-39-4272, JP-B-39-17702 and JP-B-43-13482.
• dispersions of water-insoluble or slightly soluble synthetic polymers can be added for improving the dimension stability.
• polymers comprising alkyl (meth)acrylate, alkoxyacryl (meth)acrylate or glycidyl (meth)acrylate alone or combinations thereof, or combinations of them with acrylic acid or methacrylic acid as monomer components can be used.
• Plasticizers for example, polymers or emulsions such as alkyl acrylate latexes and polyols such as trimethylol propane, can be added to the emulsion layer of the photographic material for use in the present invention to improve pressure characteristics.
• the photographic emulsion layer or other hydrophilic colloidal layers of the photographic materials produced according to the present invention may contain various surfactants for the various purposes of coating aids, static charge prevention, improvement in slipperiness, emulsified dispersion, adhesion prevention and improvement in photographic characteristics (for example, development acceleration, contrast enhancement and sensitization).
• surfactants include nonionic surfactants such as saponin (steroid series), alkylene oxide derivatives (for example, polyethylene glycol, polyethylene glycol/polypropylene glycol condensation products, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkylamines or amides, and polyethylene oxide adducts of silicones), glycidol derivatives (for example, alkenylsuccinic acid polyglycerides and alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols and alkyl esters of saccharides; anionic surfactants containing an acid group such as carboxyl, sulfo, phospho, sulfuric ester and phosphoric ester groups, such as alkylcarbonates, alkylsulfonates, alkylbenezenesulfonates, alkylnaphthalen
• Gelatin is used as a binder material for the photographic material for use in the present invention.
• hydrophilic colloids can also be used in combination therewith.
• examples of such hydrophilic colloids include gelatin derivatives, cellulose derivatives, graft polymers of gelatin and other polymers, and other proteins, saccharide derivatives, cellulose derivatives and synthetic hydrophilic polymer substances such as homopolymers or copolymers.
• Gelatin is advantageously used as a binder or a protective colloid for the photographic emulsion, but other hydrophilic colloids can also be used.
• hydrophilic colloids include gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein, cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose and cellulose sulfate, saccharide derivatives such as sodium alginate and starch derivatives, and many kinds of synthetic hydrophilic polymer substances such as homopolymers or copolymers of polyvinyl alcohol, partially acetalized polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole and polyvinylpyrazole.
• gelatin As gelatin, acid-treated gelatin, as well as lime-treated gelatin, may be used, and hydrolyzed products of gelatin and enzyme-decomposed products of gelatin can also be used.
• a homopolymer of polymethyl methacrylate or copolymers of methyl methacrylate and methacrylic acid as described in U.S. Patents 2,992,101, 2,701,245, 4,142,894 and 4,396,706, organic compounds such as starch, and finely divided grains of inorganic compounds such as silica, titanium dioxide and barium strontium sulfate can be used as matte agents.
• the grain size thereof is preferably from 1.0 to 10 ⁇ m, and particularly from 2 to 5 ⁇ m.
• the photographic emulsion layer or other layers may be colored with dyes for absorbing light within the particular wavelength range, namely conducting halation or irradiation, or providing filter layers to control spectral composition of light to be incident on the photographic emulsion layer.
• dyes include oxonol dyes having pyrazolone nuclei or barbituric acid nuclei, hemioxonol dyes, azo dyes, azomethine dyes, anthraquinone dyes, arylidene dyes, styryl dyes, triarylmethane dyes, merocyanine dyes and cyanine dyes.
• the oxonol dyes, the hemioxonol dyes and the merocyanine dyes are useful among others. Specific examples of the dyes which can be used are described in West German Patent 616,007, British Patents 584,609 and 1,117,429, JP-B-26-7777, JP-B-39-22069, JP-B-54-38129, JP-A-48-85130, JP-A-49-99620, JP-A-49-114420, JP-A-49-129537 and Photo. Abstr. , 128 ('21). In particular, for illuminated room dot to dot work photographic materials, these dyes are preferably used.
• fine solid grain dispersions of dyes described in JP-A-7-168311, pages 23 to 30 may also be used.
• dyes or ultraviolet absorbers when added to the hydrophilic colloidal layers, they may be mordanted with cationic polymers or the like.
• nonionic surfactants of the polyethylene oxide series can be preferably used in combination with polymers having cation sites.
• Preferred examples of the polymer providing the cation sites include anion conversion polymers.
• anion conversion polymers various known quaternary ammonium salt (or phosphonium salt) polymers can be used.
• the quaternary ammonium salt (or phosphonium salt) polymers are widely known as mordant polymers or antistatic agent polymers in the following publications.
• They include water-dispersed latexes as described in JP-A-59-166940, U.S. Patent 3,958,995, JP-A-55-142339, JP-A-54-126027, JP-A-54-155835, JP-A-53-30328 and JP-A-54-92274, polyvinylpyridinium salts described in U.S. Patents 2,548,564, 3,148,061 and 3,756,814, water-soluble quaternary ammonium salt polymers described in U.S. Patent 3,709,690, and water-insoluble quaternary ammonium salt polymers described in U.S. Patent 3,898,088.
• monomers each having at least 2 (preferably, 2 to 4) ethylenic unsaturated groups are copolymerized to use as crosslinked aqueous polymer latexes.
• the photographic material for use in the present invention can contain developing agents such as hydroquinone derivatives and phenidone derivatives for the various purposes of stabilizers, accelerators and the like.
• the photographic emulsion layer and other hydrophilic layers may contain inorganic or organic hardening agents.
• the hardening agents include chromium salts (such as chromium alum and chromium acetate), aldehydes (such as formaldehyde and glutaraldehyde), N-methylol compounds (such as dimethylolurea), dioxane derivatives, active vinyl compounds (such as 1,3,5-triacryloylhexahydro-s-triazine and 1,3-vinylsulfonyl-2-propanol), active halogen compounds (such as 2,4-dichloro-6-hydroxy-s-triazine) and mucohalogen acids (such as mucochloric acid). They can be used alone or in combination.
• the photographic emulsion layer and other hydrophilic layers may contain hydroquinone derivatives (so-called DIR-hydroquinone) which releases a development inhibitor corresponding to the density of images in development.
• DIR-hydroquinone hydroquinone derivatives
• the silver halide emulsion layer and other layers of the photographic material for use in the present invention preferably contain a compound having an acid group.
• the compound having an acid group include organic acids such as salicylic acid, acetic acid and ascorbic acid, and polymers or copolymers having acid monomers such as acrylic acid, maleic acid and phthalic acid as repeating units.
• organic acids such as salicylic acid, acetic acid and ascorbic acid
• polymers or copolymers having acid monomers such as acrylic acid, maleic acid and phthalic acid as repeating units.
• ascorbic acid is particularly preferred for low molecular weight compounds
• water dispersed latexes of copolymers composed of acid monomers such as acrylic acid and crosslinking monomers each having at least 2 unsaturated groups such as divinylbenzene are particularly preferred for polymers.
• the silver halide emulsions thus prepared are applied to a support such as a cellulose acetate film and a polyethylene terephthalate film by processes such as the dipping process, the air knife process, the bead process, the extrusion doctor process, and the duplicating process, followed by drying.
• Patent 4,956,257 and JP-A-1-118832 12 Redox Compounds Compounds represented by general formula (I) of JP-A-2-301743 (particularly, compound examples 1 to 50; general formulas (R-1), (R-2) and (R-3), and compounds 1 to 75 described in JP-A-3-174143, pages 3 to 20; and compounds described in JP-A-5-257239 and JP-A-4-278939 13) Monomethine Compounds Compounds of general formula (II) of JP-A-2-287532 (particularly compound examples II-1 to II-26) 14) Dihydroxybenzenes Compounds described in JP-A-3-39948, page 11, upper left column to page 12, lower left column, and EP-A-452,772
• composition of developer (1) per liter of working solution is shown below:
• the pH adjustment was carried out by use of NaOH.
• the carbonate concentration was 0.8 mol/liter, and the sulfite concentration was 0.02 mol/liter.
• the carbonate concentration and the sulfite concentration of developer (1) were changed to prepare developers (3) to (7).
• the carbonate concentration was changed by varying the amounts of sodium hydrogencarbonate and sodium carbonate at the same ratio.
• Emulsion A A method for preparing Emulsion A is described below.
• Solution 2 and solution 3 were concurrently added to solution 1 maintained at a temperature of 38°C and a pH of 4.5 with stirring over 24 minutes to form grains having a size of 0.18 ⁇ m. Subsequently, solution 4 and solution 5 were added over 8 minutes, and 0.15 g of potassium iodide was added to terminate the formation of grains.
• the grains were normally washed with water by the flocculation process, and gelatin was added thereto, followed by adjustment of pH and pAg to 5.2 and 7.5, respectively. Then, 4 mg of sodium thiosulfate, 2 mg of N,N-dimethylselenourea, 10 mg of chloroauric acid, 4 mg of sodium benzenethiosulfonate and 1 mg of sodium benzenethiosulfinate were added to conduct chemical sensitization at 55°C so as to give optimum sensitivity.
• An UL layer, an EM layer, a PC layer and an OC layer were formed, in this order from a support side, on a polyethylene terephthalate film support undercoated with a moisture-proof layer containing vinylidene chloride to prepare a sample.
• a dispersion of polyethyl acrylate was added to an aqueous solution of gelatin in an amount of 30% by weight based on gelatin, and the resulting solution was applied so as to give an amount of gelatin coated of 0.5 g/m 2 .
• the pH of the completed solution was 5.7.
• a dispersion of polyethyl acrylate was added to an aqueous solution of gelatin in an amount of 50% by weight based on gelatin, and the following surfactant (e) and 1,5-dihydroxy-2-benzaldoxime were added so as to be applied in amounts of 5 mg/m 2 and 10 mg/m 2 , respectively.
• the resulting solution was applied so as to give an amount of gelatin coated of 0.5 g/m 2 .
• Gelatin 0.5 g/m 2
• 0.1 g/m 2 of methanol silica 100 mg/m 2 of polyacrylamide, 20 mg/m 2 of silicone oil, 5 mg/m 2 of the fluorine surfactant represented by the following structural formula (f) as a coating aid, 100 mg/m 2 of sodium dodecylbenezenesulfonate and 20 mg/m 2 of the compound represented by the following structural formula (g) were applied.
• the coated sample had a back layer and a back protective layer having the following compositions:
• Emulsion B was prepared in the same manner as with emulsion A, except that the addition amount of the sodium thiosulfate was changed to 2 mg per mol of silver, and that no selenium sensitizer was used.
• a sample was prepared in the same manner as in the preparation of photographic material (1) with the exception that the sensitizing dye of photographic material (1) was substituted by S-2 (5X10 -4 mol/mol Ag) and S-3 (5X10 -4 mol/mol Ag) shown below, and that emulsion B was used as an emulsion for the EM layer.
• a 1.5% aqueous solution of gelatin having a pH of 2.0 maintained at 40°C which contains sodium chloride, 3X10 -5 mol per mol of silver of sodium benzenesulfonate and 5X10 -3 mol of 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene, and an aqueous solution of sodium chloride containing 2.0X10 -6 mol per mol of silver of K 2 Ru(NO)Cl 5 were concurrently added by the double jet method at a potential of 95 mV over 3 minutes and 30 seconds by half of the silver amount of final grains to prepare core grains having a size of 0.12 ⁇ m.
• the following support was coated with EM, PC and OC layers in this order.
• the following compounds were added to the above-described emulsion C, and the resulting emulsion was applied so as to give a coating amount of gelatin of 0.9 g/m 2 and a coating amount of silver of 2.7 g/m 2 , thereby forming a silver halide emulsion layer.
• the opposite surface of the support was concurrently coated with the following coating solutions for a conductive layer and a back layer.
• a first undercoat layer and a second undercoat layer having the following compositions were formed on both faces of a biaxially oriented polyethylene terephthalate support (thickness: 100 ⁇ m).
• Core/Shell Type Vinylidene Chloride Copolymer (1) 15 g 2,4-Dichloro-6-hydroxy-s-triazine 0.25 g Fine Polystyrene Particles (mean particle size: 3 ⁇ m) 0.05 g Compound-M 0.20 g Colloidal Silica (Snowtex ZL; grain size: 70 to 100 ⁇ m; manufactured by Nissan Chemical Industries Ltd.) 0.12 g Water to make 100 g
• This coating solution was applied so as to give a dry film thickness of 0.1 ⁇ m at a drying temperature of 170°C for 2 minutes. Thus, a sample was prepared.
• a KI solution was added in an amount of 1X10 -3 mol per mol of silver to conduct conversion, and the grains were normally washed with water by the flocculation process.
• Gelatin was added thereto in an amount of 40 g per mol of silver, followed by adjustment of pH and pAg to 5.9 and 7.5, respectively.
• 3 mg per mol of silver of sodium benzenethiosulfonate, 1 mg of sodium benzenesulfinate, 2 mg of sodium thiosulfate, 2 mg of a compound represented by the following structural formula (h) and 8 mg of chloroauric acid were added, and heated at 60°C for 70 minutes to conduct chemical sensitization.
• the pH of the coating solution was adjusted to 5.6.
• a compound represented by (n), a compound represented by (o) and a dispersion of polyethyl acrylate were added so as to be applied in amounts of 10 mg/m 2 , 100 mg/m 2 and 300 mg/m 2 , respectively, to prepare a PC solution.
• an irregular SiO 2 matte agent having a mean grain size of about 3.5 ⁇ m, colloidal silica (Snowtex C manufactured by Nissan Chemical Industries Ltd.), liquid paraffin, the fluorine surfactant represented by the following structural formula (p) and sodium p-dodecylbenezenesulfonate as coating aids were added so as to be applied in amounts of 50 mg/m 2 , 100 mg/m 2 , 30 mg/m 2 , 5 mg/m 2 and 30 mg/m 2 , respectively, to prepare an OC solution.
• the pH of an emulsion surface of the resulting sample was 5.8.
• a back layer was formed according to the following formulation.
• Photographic materials (1) to (4) were processed with developers (1) to (5).
• fixing solution (1) was used in common. Combinations of the photographic materials and the developers used are shown in Table 10.
• Each of the photographic materials was processed with an FG-680AG automatic processor (manufactured by Fuji Photo Film Co., Ltd.) charged with the developer and the fixing solution at a developing temperature of 35°C at a fixing temperature of 34°C for a developing time of 20 seconds.
• the sensitivity of sensitometry was relatively compared, taking as 100 a sensitivity at the time when each photographic material was processed with developer (1).
• the sensitivity evaluation point was indicated using an exposure amount giving a density of 1.5.
• ⁇ (gamma) was indicated using a slope between two points, 0.3 and 3.0 in density.
• the exposure conditions of the respective photographic materials were as follows:
• Sensitivity ⁇ (Gamma) Remark At Running Start On Termination At Running Start On Termination 1 1 1 1 100 71 18 9.5 Comparison 2 1 2 2 100 87 9.0 7.5 Comparison 3 1 1 3 100 91 18 16 Invention 4 2 1 3 100 93 20 17 Invention 5 3 1 3 100 95 13 11 Invention 6 4 1 3 100 91 17 16 Invention 7 2 1 1 100 78 20 10 Comparison 8 3 1 1 100 83 13 8.0 Comparison 9 4 1 1 100 78 17 9.5 Comparison 10 1 4 5 100 48 17 6.5 Comparison 11 2 4 5 100 43 19 6.8 Comparison
• test Nos. 3 to 6 of the present invention were reduced in changes in sensitivity and in a reduction in contrast ( ⁇ ) due to the running, exhibiting excellent characteristics.
• Test No. 2 in which the 3-pyrazolidone compound was used as the auxiliary developing agent is unfavorably low in contrast from the start of the running.
• a silver stain inhibitor selected from the exemplified compounds of general formula (1) was added in an amount shown in Table 11 to each of the starting developing solution and the developing replenisher. It was added to both the starting developing solution and the developing replenisher in the same amount.
• 300 m 2 of a consumption photographic material was processed, while replenishing a developing replenisher in the same manner as in Example 1, using an unexposed photographic material different from Example 1.
• Silver stain which adhered to the first processed photographic material on the day after the day when the consumption was conducted was evaluated. No stain adhered at the start, so that only results of evaluation of silver stain on the termination are shown in Table 11.
• fixing solution (2) was used, and the replenishment rate thereof was 150 ml/m 2 .
• the photographic material used was photographic material (1). TABLE 11 Test No. Developing Solution No. Silver Stain Inhibitor Silver Stain Remark Starting Solution Replenisher Compound No. Amount Added (mmol/l) 12 1 3 - - ⁇ Comparison 13 1 3 11 0.5 ⁇ Invention 14 1 3 23 0.5 o Invention 15 1 3 30 0.5 o Invention 16 6 7 11 0.5 ⁇ Comparison 17 6 7 23 0.5 ⁇ Comparison 18 1 3 77 0.5 o Invention 19 1 3 108 0.5 o Invention 20 1 3 117 0.5 o Invention

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• 1997
  • 1997-02-07 EP EP97101987A patent/EP0789271A1/de not_active Withdrawn

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