EP0436027B1 - Method of treating silver halide photographic material - Google Patents

Method of treating silver halide photographic material Download PDF

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EP0436027B1
EP0436027B1 EP90909370A EP90909370A EP0436027B1 EP 0436027 B1 EP0436027 B1 EP 0436027B1 EP 90909370 A EP90909370 A EP 90909370A EP 90909370 A EP90909370 A EP 90909370A EP 0436027 B1 EP0436027 B1 EP 0436027B1
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group
compounds
compound
substituted
hydrogen atom
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English (en)
French (fr)
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EP0436027A1 (en
EP0436027A4 (en
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Eiichi Fuji Photo Film Co. Ltd. Okutsu
Hisashi Fuji Photo Film Co. Ltd. Okamura
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/38—Fixing; Developing-fixing; Hardening-fixing
    • G03C5/386—Hardening-fixing

Definitions

  • This invention relates to a method for forming ultra-high-contrast negative image using a silver halide photographic material. More particularly, it relates to a processing method of an ultra-high-contrast negative type photographic material for use in a silver halide photographic material used for photomechanical process.
  • the originals in line camera work in particular are formed by sticking e.g. phototypeset letters, handwritten letters, illustrations or dotted photographs. Accordingly, images having e.g. different densities and line widths coexist in the originals, and it is highly demanded to provide process cameras, photographic materials or image forming methods for finishing the originals with good reproducibility.
  • the enlargement (spread) or reduction (choke) of halftone photographs is widely carried out to make plates for catalogs or large-sized posters.
  • screen ruling becomes loose and the photographing of out-of-focus dots is made, while in reduction, screen ruling/inch is larger than that of the original and the photographing of finer dots is made. Accordingly, it is demanded to provide an image forming method which has a still wider latitude for halftone photographing to keep the reproducibility of halftone gradation and which can form high-contrast image.
  • Halogen lamp or xenon lamp is used as a light source for process cameras.
  • photographic materials are subjected to ortho-sensitization to obtain photographing sensitivity for these light sources.
  • ortho-sensitized photographic materials are more intensively affected by chromatic aberration of a lens and image quality is liable to be deteriorated. The deterioration is particularly remarkable with xenon lamp light source.
  • These new image forming systems are characterized by that silver iodobromide and silver chloroiodobromide can also be used, while only silver chlorobromide having a high silver chloride content can be used in conventional ultra-high-contrast image formation.
  • light-sensitive material for daylight refers to light-sensitive materials which allow light containing no ultraviolet light component and having a wavelength of substantially at least 400 nm as safelight to be used stably over a long period of time.
  • Light-sensitive materials for daylight used in page make-up stage and dot to dot work stage are light-sensitive materials which are utilized for carrying out negative image/positive image conversion or positive image/positive image conversion by using processed films having letters or halftone images formed thereon as the originals, bringing these originals into closely contact with light-sensitive materials for dot to dot work and exposing them.
  • the light-sensitive materials are demanded to have such performances that (1) negative image/positive image conversion of halftone images, line works and letter images can be made according to dot area, line width and letter image width; and (2) the tone control of halftone images and the line width control of letter line images can be made.
  • a film (b) having letters or line works formed thereon (the line original) and a film (d) having halftone image formed thereon (the halftone original) are laminated onto transparent or semitransparent laminating bases (a) and (c) (generally a polyethylene terephthalate film of about 100 ⁇ m being used), respectively.
  • the resulting laminates are superposed with each other to obtain the original.
  • the emulsion surface of a light-sensitive material (e) for dot to dot work is brought into closely contact with the halftone original (d), and exposure is then carried out.
  • the line original is to be subjected out-of-focus exposure through the spacers of the laminating base (c) and the halftone original (d) and the printing image width of the transparent line work portions becomes narrow. The deterioration of the quality of the superimposed letter image is caused thereby.
  • JP-A-62-80640 Method for solving the above-described problem in the ultra-high-contrast image forming systems are disclosed in JP-A-62-80640 (the term "JP-A” as used herein means an "unexamined published Japanese patent application"), JP-A-62-235938, JP-A-62-235939, JP-A-63-104046, JP-A-63-103235, JP-A-63-296031, JP-A-63-314541 and JP-A-64-13545.
  • JP-A-62-80640 the term "JP-A" as used herein means an "unexamined published Japanese patent application”
  • JP-A-62-235938 JP-A-62-235939
  • JP-A-61-213847, U.S. Patent 4,684,604, JP-A-64-72140 and JP-A-64-72139 disclose the use of redox compounds which release a development restrainer when oxidized in silver halide photographic materials.
  • U.S. Patent 4,569,904 discloses a method for developing an exposed negative silver halide photographic light-sensitive material in the presence of a hydrazine derivative, comprising treating the material with a developer containing at least a developing agent, not less than 0.25 mol/l of a sulfite preservative and not less than 0.1 mol/l of a compound having an acid dissociation constant of from 1x10 -11 to 3x10 -13 , and having a pH of from 10.5 to 12.3.
  • European Patent 21,005 (corresponding to JP-A-55-153939) discloses an aqueous hardening-fixing bath containing 0.015 to 0.1 mol/l of a water-soluble aluminum salt and a formiate for processing an exposed and developed photographic material.
  • JP-A-60-136741 discloses a method for processing a photosensitive material wherein an exposed photosensitive silver halide material is developed with a developing solution having a pH of from 10.7 to 12.5 and containing dihydroxybenzenes and optionally 3-pyrazolidones, and fixed with a fixing solution containing an aluminum salt.
  • JP-A-48-5502 discloses the use of phenol compounds in a photographic material.
  • An object of the present invention is to provide a stable rapid processing method of a silver halide photographic material used in the field of photomechanical process, particularly a photographic material having excellent original reproducibility in the photographing of the letter original and the halftone original.
  • Another object of the present invention is to provide a stable rapid processing method of a photographic material which gives superimposed letter image of excellent quality and is a light-sensitive material for contact dot to dot work, which is capable of being handled under environmental conditions which are allowed to be called daylight used in the field of photomechanical process.
  • the objects of the present invention have been achieved by providing a processing method of a silver halide photographic material characterized by processing a light-sensitive silver halide photographic material containing a hydrazine nucleating agent and a redox compound capable of releasing a development restrainer when oxidized, with a developing solution containing a phenol having an acid dissociation constant of 1x10 -11 to 3x10 -13 in an amount of at least 0.05 mol/l and then processing it with an acid hardening fixer containing a water-soluble aluminum compound.
  • redox compound examples include compounds having hydroquinones, catechols, naphthohydroquinones, aminophenols, pyrazolidones, hydrazines, hydroxylamines and reductones as redox groups. More preferred redox compounds are compounds having hydrazines as redox groups. Particularly preferred examples of the redox compounds are compounds represented by the following general formula (I). The compounds are compounds which are oxidized by the oxidation products of developing agents and then release a development restrainer by a nucleophilic reaction, a hydrolysis reaction or an elimination reaction.
  • both A 1 and A 2 represent hydrogen atom, or one of A 1 and A 2 represents hydrogen atom and the other represents a residue of a sulfinic acid or wherein R 0 represents an alkyl group, an alkenyl group, an aryl group, an alkoxy group or an aryloxy group and l represents 1 or 2; A 1 may be combined together with (Time) t to form a ring; Time represents a divalent linking group; t represents 0 or 1; PUG represents a development restrainer; V represents carbonyl group, a sulfonyl group, a sulfoxy group, (wherein R 1 represents an alkoxy group or an aryloxy group), an iminomethylene group or a thiocarbonyl group; and R represents an aliphatic group, an aromatic group or a heterocyclic group.
  • a 1 and A 2 preferably are each hydrogen atom, an alkylsulfonyl group having not more than 20 carbon atoms, an arylsulfonyl group having not more than 20 carbon atoms (preferably phenylsulfonyl group or a substituted phenylsulfonyl group wherein the sum of Hammett's substituent constant is at least -0.5) or [R 0 is preferably a straight-chain, branched or cyclic alkyl group having not more than 30 carbon atoms, an alkenyl group, an aryl group (preferably phenyl group or a substituted phenyl group wherein the sum of Hammett's substituent constant is at least -0.5), an alkoxy group (e.g., ethoxy group) or an aryloxy group (preferably a monocyclic aryloxy group).
  • These groups may have one or more substituent groups which may be further substituted, and examples of said substituent groups include an alkyl group, an aralkyl group, an alkenyl group, an alkinyl group, an alkoxy group, an aryl group, a substituted amino group, an acylamino group, a sulfonylamino group, a ureido group, a urethane group, an aryloxy group, a sulfamoyl group, a carbamoyl group, an alkylthio group, an arylthio group, a sulfonyl group, a sulfinyl group, hydroxyl group, a halogen atom, cyano group, sulfo group, carboxyl group, an aryloxycarbonyl group, an acyl group, an alkoxycarbonyl group, an acyloxy group, a carbonamido group, a sulfona
  • Examples of the residue of a sulfinic acid represented by A 1 and A 2 include concretely those described in U.S. Patent 4,478,928.
  • a 1 and A 2 are each hydrogen atom.
  • Time is a divalent linking group and may have a timing controlling function, and t is 0 or 1.
  • t 0
  • PUG is bonded directly to V.
  • the divalent linking group represented by Time is a group which releases PUG from Time-PUG through one-stage reaction or multi-stage reaction, said Time-PUG being released from the oxidant of the parent redox nucleus.
  • Examples of the divalent linking group represented by Time include those which release a photographically useful group (PUG) by the intramolecular ring closure reaction of p-nitrophenoxy derivatives as described in U.S. Patent 4,248,962 (JP-A-54-145135); those which release PUG by intramolecular ring closure reaction after ring cleavage as described in U.S. Patents 4,310,612 (JP-A-55-53330) and 4,358,252; those which release PUG with the formation of acid anhydrides by the intramolecular ring closure reaction of carboxyl group of monoesters of succinic acid or analogs thereof as described in U.S.
  • PUG photographically useful group
  • Patent 4,420,554 JP-A-57-136640), JP-A-57-135945, JP-A-57-188035, JP-A-58-98728 and JP-A-58-209737; those which release PUG by the intramolecular ring closure reaction of oxy group formed by electron transfer to carbonyl group conjugated with nitrogen atom of a nitrogen-containing heterocyclic ring as described in JP-A-57-56837; those which release PUG with the formation of aldehydes as described in U.S.
  • Patent 4,146,396 JP-A-52-90932), JP-A-59-93442 and JP-A-59-75475; those which release PUG with the decarboxylation of carboxyl group as described in JP-A-51-146828, JP-A-57-179842 and JP-A-59-104641; those which has a structure of (wherein R a and R b are each a substituent group) and release PUG with the formation of aldehydes subsequent to decarboxylation; those which release PUG with the formation of an isocyanate as described in JP-A-60-7429; and those which release PUG by coupling reaction with the oxidants of color developing agents as described in U.S. Patent 4,438,193.
  • (*) represents a position where (Time -PUG is bonded to V in general formula (I) and (*)(*) represents a position where (Time) t is bonded to PUG.
  • PUG represents a group having a development-restraining effect as (Time -PUG or PUG.
  • Development restrainers represented by PUG or (Time -PUG are conventional development restrainers having hetero-atom and are bonded through hetero-atom. For example, these development restrainers are described in C.E.K. Mees and T.H. James, The Theory of the Photographic Process, third edition, pages 344-346 (1966 Macmillan).
  • the development restrainers include concretely mercaptotetrazoles, mercaptotriazoles, mercaptoimidazoles, mercaptopyrimidines, mercaptobenzimidazoles, mercaptobenzthiazoles, mercaptobenzoxazoles, mercaptothidiazoles, benztriazoles, benzimidazoles, indazoles, adenines, guanines, tetrazoles, tetraataindenes, triazaindenes and mercaptoaryls.
  • the development restrainers represented by PUG may have one or more substituent groups which may be further substituted.
  • substituent groups include an alkyl group, an aralkyl group, an alkenyl group, an alkinyl group, an alkoxy group, an aryl group, a substituted amino group, an acylamino group, a sulfonylamino group, a ureido group, a urethane group, an aryloxy group, a sulfamoyl group, a carbamoyl group, an alkylthio group, an arylthio group, a sulfonyl group, a sulfinyl group, hydroxyl group, a halogen atom, cyano group, sulfo group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an acyl group, an acyloxy group, a carbonamido group, a sulfonamido group, carboxyl group, sulfoxy group, a phosphono group
  • Preferred substituent groups are nitro group, sulfo group, carboxyl group, a sulfamoyl group, a phosphono group, a phosphinyl group and a sulfonamido group.
  • Typical development restrainers include the following compounds.
  • V is carbonyl group, a sulfonyl group, a sulfoxy group, (wherein R 1 is an alkoxy group or an aryloxy group), an iminomethylene group or a thiocarbonyl group.
  • R 1 is an alkoxy group or an aryloxy group
  • V is carbonyl group.
  • the aliphatic group represented by R is a straight-chain, branched or cyclic alkyl, alkenyl or alkinyl group having preferably 1 to 30 carbon atoms, particularly preferably 1 to 20 carbon atoms.
  • the branched alkyl group may be cyclized so as to form a saturated heterocyclic ring having one or more heteroatoms as the members of the ring.
  • Examples of the aliphatic group include methyl group, t-butyl group, n-octyl group, t-octyl group, cyclohexyl group, hexenyl group, pyrrolidyl group, tetrahydrofuryl group and n-dodecyl group.
  • the aromatic group is a monocyclic or bicyclic aryl group such as phenyl group and naphthyl group.
  • the heterocyclic group is preferably a 3-membered to 10-membered saturated or unsaturated heterocyclic ring containing at least one atom of N, O and S atoms and may be a monocyclic ring or a condensed ring with other aromatic ring or heterocyclic ring.
  • the heterocyclic ring is a 5-membered or 6-membered aromatic heterocyclic ring such as pyridine ring, imidazolyl group, quinolinyl group, benzimidazolyl group, pyrimidinyl group, pyrazolyl group, isoquinolinyl group, benzthiazolyl group and thiazolyl group.
  • R may have one or more substituent groups which may be further substituted.
  • substituent groups include an alkyl group, an aralkyl group, an alkenyl group, an alkinyl group, an alkoxy group, an aryl group, a substituted amino group, an acylamino group, a sulfonylamino group, a ureido group, a urethane group, an aryloxy group, a sulfamoyl group, a carbamoyl group, an alkylthio group, an arylthio group, a sulfonyl group, a sulfinyl group, hydroxyl group, a halogen atom, cyano group, sulfo group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an acyl group, an acyloxy group, a carbonamido group, a sulfonamido group, carboxy group and phosphoric amido group.
  • R or (Time -PUG may have a ballast group conventionally used in non-mobile photographic additives such as couplers or a group which accelerate the adsorption of the compounds of general formula (I) on silver halide.
  • the ballast group is an organic group which give sufficient molecular weight so that the compounds of general formula (I) are substantially not allowed to be diffused in other layers or processing solutions.
  • the ballast group is composed of an alkyl group, an aryl group, a heterocyclic group, an ether group, a thioether group, an amido group, a ureido group, a urethane group or a sulfonamido group singly or in combination.
  • Preferred ballast group is a ballast group having a substituted benzene ring. Ballast groups having a branched alkyl group-substituted benzene ring are particularly preferred.
  • cyclic thioamido groups such as 4-thiazoline-2-thione, 4-imidazoline-2-thione, 2-thiohydantoin, rhodanine, thiobarbituric acid, tetrazoline-5-thione, 1,2,4-triazoline-3-thione, 1,3,4-oxazoline-2-thione, benzimidazoline-2-thione, benzoxazoline-2-thione, benzothiazoline-2-thione, thiotriazine and 1,3-imidazoline-2-thione, chain thioamido groups, aliphatic mercapto groups, aromatic mercapto groups, heterocyclic mercapto groups (when atom adjacent to carbon atom to which -SH group is bonded is nitrogen group, the group and said cyclic thioamido group exist in a tautomeric form and examples thereof include those described above), groups having disulfon of the group having disulfon of the group, 4-thiazoline-2-
  • substituent groups examples include those already described above in the definition of the substituent groups for R.
  • the redox compounds used in the present invention are preferably used in an amount of 1.0 ⁇ 10 -7 to 1.0 ⁇ 10 -3 mol/m 2 , preferably 1.0 ⁇ 10 -6 to 1.0 ⁇ 10 -4 mol/m 2 .
  • the redox compounds can be used by dissolving them in appropriate water-miscible organic solvents such as alcohols (e.g., methanol, ethanol, propanol, fluorinated alcohols), ketones (e.g., acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide or methyl cellosolve.
  • alcohols e.g., methanol, ethanol, propanol, fluorinated alcohols
  • ketones e.g., acetone, methyl ethyl ketone
  • dimethylformamide dimethyl sulfoxide or methyl cellosolve.
  • the redox compounds may be used in the form of emulsified dispersions prepared by dissolving them in oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate with an auxiliary solvent such as ethyl acetate or cyclohexanone and forming mechanically the emulsified dispersions by well-known emulsifying dispersion method.
  • the redox compounds may be used by dispersing the powder thereof in water by using a ball mill, a colloid mill or ultrasound by well-known emulsifying dispersion method.
  • a layer containing the redox compound used in the present invention may be provided above or under a light-sensitive emulsion layer containing a hydrazine nucleating agent.
  • the layer containing the redox compound may contain further light-sensitive or light-insensitive silver halide emulsion grains.
  • An interlayer containing gelatin or a synthetic polymer e.g., polyvinyl acetate, polyvinyl alcohol
  • the hydrazine nucleating agent (hereinafter referred to as hydrazine derivative) used in the present invention is a compound which exhibits a function capable of fogging silver halide by a nucleophilic reaction, a hydrolysis reaction or an elimination reaction after the compound is oxidized by the oxidation product of a developing agent.
  • hydrazine derivative a compound which exhibits a function capable of fogging silver halide by a nucleophilic reaction, a hydrolysis reaction or an elimination reaction after the compound is oxidized by the oxidation product of a developing agent.
  • compounds represented by the following general formula (II) are preferred.
  • R 1 represents an aliphatic group or an aromatic group
  • R 2 represents hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group, a carbamoyl group or an oxycarbonyl group
  • G 1 represents carbonyl group, a sulfonyl group, a sulfoxy group, a group of or an iminomethylene group
  • both A 1 and A 2 are hydrogen atom or one of A 1 and A 2 represents 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 straight-chain, branched or cyclic alkyl group having preferably 1 to 30 carbon atoms, particularly preferably 1 to 20 carbon atoms.
  • the branched alkyl group may be cyclized so as to form a saturated heterocyclic ring having one or more heteroatoms as the members of the ring.
  • the alkyl group may have one or more substituent groups such as an aryl group, an alkoxy group, a sulfoxy group, a sulfonamido group and a carbonamido group.
  • the aromatic group represented by R 1 in general formula (II) is preferably a monocyclic or bicyclic aryl or unsaturated heterocyclic group.
  • the unsaturated heterocyclic group may be condensed with a monocyclic or bicyclic aryl group to form a hetero-aryl group.
  • aromatic group examples include benzene ring, naphthalene ring, pyridine ring, pyrimidine ring, imidazole ring, pyrazole ring, quinoline ring, isoquinoline ring, benzimidazole ring, thiazole ring and benzthiazole ring.
  • groups having benzene ring are preferred.
  • R 1 is an aryl group.
  • the aryl group or the unsaturated heterocyclic represented by R 1 may be substituted.
  • substituent groups include an alkyl group, an aralkyl group, an alkenyl group, an alkinyl group, an alkoxy group, an aryl group, a substituted amino group, an acylamino group, a sulfonylamino group, a ureido group, a urethane group, an aryloxy group, a sulfamoyl group, a carbamoyl group, an alkylthio group, an arylthio group, a sulfonyl group, a sulfinyl group, hydroxyl group, a halogen atom, cyano group, sulfo group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an acyl group, an alkoxycarbonyl group, an acyloxy group, a carbonamido group
  • Preferred substituent groups are a straight-chain, branched or cyclic alkyl group (having preferably 1 to 20 carbon atoms), an aralkyl group (preferably, a monocyclic or bicyclic group having an alkyl portion of 1 to 3 carbon atoms), an alkoxy group (having preferably 1 to 20 carbon atoms), a substituted amino group (preferably an amino group substituted by an alkyl group having 1 to 20 carbon atoms), an acylamino group (having preferably 2 to 30 carbon atoms), a sulfonamido group (having preferably 1 to 30 carbon atoms), a ureido group (having preferably 1 to 30 carbon atoms), a phosphoric amido group (having preferably 1 to 30 carbon atoms), etc.
  • the alkyl group represented by R 2 in general formula (II) is preferably an alkyl group having 1 to 4 carbon atoms which may be substituted.
  • substituent groups include a halogen atom, cyano group, carboxy group, sulfo group, an alkoxy group, phenyl group and a sulfonyl group.
  • the aryl group is preferably a monocyclic or bicyclic group such as a group having benzene ring.
  • the aryl group may be substituted.
  • substituent groups include a halogen atom, an alkyl group, cyano group, carboxyl group, sulfo group and a sulfonyl group.
  • the alkoxy group is preferably an alkoxy group having 1 to 8 carbon atoms and may be substituted by a halogen atom or an aryl group.
  • the aryloxy group is preferably a monocyclic group and may be substituted by e.g. a halogen atom.
  • the amino group is preferably unsubstituted amino group, an alkylamino group having 1 to 10 carbon atoms or an arylamino group.
  • the amino group may be substituted by an alkyl group, a halogen atom, cyano group, nitro group or carboxy group.
  • the carbamoyl group is preferably unsubstituted carbamoyl group, an alkylcarbamoyl group having 1 to 10 carbon atoms or an arylcarbamoyl group.
  • the carbamoyl group may be substituted by an alkyl group, a halogen atom, cyano group or carboxy group.
  • the oxycarbonyl group is preferably an alkoxycarbonyl group having 1 to 10 carbon atoms or aryloxycarbonyl group.
  • the oxycarbonyl group may be substituted by an alkyl group, a halogen atom, cyano group or nitro group.
  • R 2 there are preferred hydrogen atom, an alkyl group (e.g., methyl group, trifluoromethyl group, 3-hydroxypropyl group, 3-methanesulfonamidopropyl group, phenylsulfonylmethyl group), an aralkyl group (e.g., o-hydroxybenzyl group) and an aryl group (e.g., phenyl group, 3,5-dichlorophenyl group, o-methanesulfonamidophenyl group, 4-methanesulfonylphenyl group), with hydrogen atom being particularly preferred when G 1 is carbonyl group.
  • an alkyl group e.g., methyl group, trifluoromethyl group, 3-hydroxypropyl group, 3-methanesulfonamidopropyl group, phenylsulfonylmethyl group
  • an aralkyl group e.g., o-hydroxybenzyl group
  • R 2 is preferably an alkyl group (e.g., methyl group), an aralkyl group (e.g., o-hydroxyphenylmethyl group), an aryl group (e.g., phenyl group) or a substituted amino group (e.g., dimethylamino group).
  • alkyl group e.g., methyl group
  • aralkyl group e.g., o-hydroxyphenylmethyl group
  • an aryl group e.g., phenyl group
  • a substituted amino group e.g., dimethylamino group
  • R 2 is preferably diaminobenzyl group or methylthiobenzyl group.
  • G 1 is a group of R 2 is preferably methoxy group, ethoxy group, butoxy group, phenoxy group or phenyl group with phenoxy group being most preferred.
  • R 2 is preferably methyl group, ethyl group or a substituted or unsubstituted phenyl group.
  • substituent groups for R 2 include those already described above in the definition of the substituent groups for R 1 .
  • G 1 in general formula (II) is carbonyl group.
  • R 2 may be a group which cause the cleavage of G 1 -R 2 moiety from the remainder of the molecule and allow a cyclization reaction to take place to thereby form a cyclic structure containing the atoms of the -G 1 -R 2 moiety.
  • a such a group can be represented, for example, by the following general formula (a).
  • Z 1 may be a functional group such as OH, SH, NHR 4 (wherein R 4 is hydrogen atom, an alkyl group, an aryl group, -COR 5 or -SO 2 R 5 , and R 5 is hydrogen atom, an alkyl group, an aryl group, a heterocyclic group) or COOH which can be directly reacted with G 1 (OH, SH, NHR 4 and -COOH may be temporarily protected with an alkyl group so as to allow these groups to be reformed by hydrolysis), or a functional group such as (wherein R 6 and R 7 are each hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group) which can be reacted with G 1 in the presence of a nucleophilic reagent such as hydroxyl ion or a sulfite ion.
  • a nucleophilic reagent such as hydroxyl ion or a sulfite ion.
  • the ring formed by G 1 , R 3 and Z 1 is preferably a 5-membered or 6-membered ring.
  • R b 1 to R b 4 may be the same or different groups and each is hydrogen atom, an alkyl group (having preferably 1 to 12 carbon atoms), an alkenyl group (having preferably 2 to 12 carbon atoms) or an aryl group (having preferably 6 to 12 carbon atoms);
  • B is an atomic group required for the formation of a 5-membered or 6-membered ring which may be substituted; and m and n are each 0 or 1 and (n+m) is 1 or 2.
  • Examples of the 5-membered or 6-membered ring formed by B include cyclohexene ring, cycloheptene ring, benzene ring, naphthalene ring, pyridine ring and quinoline ring.
  • Z 1 is as defined above in general formula (a).
  • R c 1 and R c 2 may be the same or different groups and each is hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a halogen atom
  • R c 3 is hydrogen atom, an alkyl group, an alkenyl group or an aryl group
  • p is 0, 1 or 2
  • q is 1 to 4
  • R c 1 , R c 2 and R c 3 may be combined together to form a ring, so long as the ring has a structure which allows the intramolecular nucleophilic attack of Z 1 on G 1 to be made.
  • R c 1 and R c 2 are each preferably hydrogen atom, a halogen atom or an alkyl group, and R c 3 is preferably an alkyl group or an aryl group.
  • q is 1 to 3.
  • p is 1 or 2.
  • p is 0 or 1 and when q is 3, p is 0 or 1.
  • CR c 1 R c 2 may be the same or different groups.
  • Z 1 is as defined above in general formula (a).
  • a 1 and A 2 are preferably each hydrogen atom, an alkylsulfonyl group having not more than 20 carbon atoms, an arylsulfonyl group having not more than 20 carbon atoms (preferably phenylsulfonyl group or a substituted phenylsulfonyl group wherein the sum of Hammett's substituent constant is at least -0.5) or an acyl group having not more than 20 carbon atoms [preferably benzoyl group, a substituted benzoyl group wherein the sum of Hammett's substituent constant is at least -0.5 or a straight-chain, branched or cyclic unsubstituted or substituted aliphatic acyl group (examples of substituent groups include a halogen atom, an ether group, a sulfonamido group, a carbonamido group, hydroxyl group, carboxy group and sulfo group)].
  • a 1 and A 2 preferably are each hydrogen atom.
  • R 1 or R 2 in general formula (II) may have a ballast group therein conventionally used in non-mobile photographic additives such as couplers.
  • the ballast group is a group having at least 8 carbon atoms which is relatively inert to photographic characteristics.
  • the ballast group can be chosen from among an alkyl group, an alkoxy group, phenyl group, an alkylphenyl group, phenoxy group and an alkylphenoxy group.
  • a group which increases adsorption on the surfaces of silver halide grains may be incorporated into the structure of R 1 or R 2 in general formula (II).
  • adsorption groups include groups such as a thiourea group, a heterocyclic group, a thioamido group, a mercaptoheterocyclic group and a triazole group described in U.S.
  • the hydrazine derivatives are contained in silver halide emulsion layers of the photographic material.
  • the hydrazine derivatives may be contained in light-insensitive hydrophilic colloid layers (e.g., protective layer, interlayer, filter layer, antihalation layer).
  • hydrophilic colloid layers e.g., protective layer, interlayer, filter layer, antihalation layer.
  • the compounds to be used are water-soluble, they in the form of an aqueous solution are added to a hydrophilic colloid solution, and when the compounds are difficultly soluble in water, a solution thereof in a water-miscible organic solvent such as an alcohol, an ester or a ketone is added to the hydrophilic colloid solution.
  • the addition may be made at any stage before coating after the commencement of chemical ripening, but it is preferred that the addition is made before coating after the completion of chemical ripening. It is particularly preferred that the compounds are added to coating solutions prepared for coating.
  • the optimum amount of the hydrazine derivative content is chosen according to the grain size and halogen composition of the silver halide emulsion, the method and degree of chemical sensitization, the relationship between the layer in which the compound is contained and the silver halide emulsion layer or the type of anti-fogging agent. Test methods for choosing the optimum amount are well known by those skilled in the art.
  • the hydrazine derivatives are used in an amount of preferably 10 -6 to 1 ⁇ 10 -1 mol, particularly preferably 10 -5 to 4 ⁇ 10 -2 mol per mol of silver halide.
  • Silver halide emulsions which are used in the present invention may have any composition of e.g. silver chloride, silver bromide, silver chlorobromide, silver iodobromide or silver iodochlorobromide. However, silver iodobromide is preferred.
  • the content of silver iodide is preferably not higher than 10 mol%, particularly preferably 0.1 to 3.5 mol%.
  • the mean grain size of silver halide used in the present invention is preferably fine grain size (e.g., not larger than 0.7 ⁇ m) and particularly preferably not larger than 0.5 ⁇ m. Though there is basically no limitation with regard to grain size distribution, monodisperse system is preferable.
  • the term "monodisperse system” as used herein means that it is composed of grains at least 95% (in terms of weight or the number of grains) of which have a grain size of within mean grain size ⁇ 40%.
  • the silver halide grains in the photographic emulsions may have regular crystal form such as cube, octahedron, tetradecahedron or rhombic dodecahedron, particularly preferably cube or tetradecahedron, irregular crystal form such as sphere, plate or tabular form having an aspect ratio of 3 to 20 or a composite form of these crystal forms.
  • the interior and surface layer of the silver halide grain may be composed of a uniform phase or separate phases. Two or more kinds of silver halide emul sions separately prepared may be mixed and used.
  • Cadmium salt, sulfite, lead salt, thallium salt, rhodium salt or complex salt thereof, iridium salt or complex salt thereof may be allowed to coexist during the course of the formation of silver halide grains used in the present invention or the physical ripening thereof.
  • Silver halide particularly suitable for use in the present invention is a silver haloiodide which is prepared by allowing an iridium salt or a complex salt thereof in an amount of 10 -3 to 10 -5 mol per mol of silver to coexist and in which the silver iodide content on the surface of grain is higher than the average silver iodide content of grain.
  • an emulsion containing such a silver haloiodide is used, photographic characteristics having further higher sensitivity and high gamma value can be obtained.
  • an iridium salt in an amount described above is added before the completion of physical ripening, particularly during the course of the formation of grains in the above-described preparation of the silver halide emulsion.
  • the iridium salt used above is a water-soluble iridium salt or iridium complex salt.
  • examples thereof include iridium trichloride, iridium tetrachloride, potassium hexachloroiridate(III), potassium hexachloroiridate(IV) and ammonium hexachloroiridate(III).
  • the emulsion used in the present invention may not be subjected to chemical sensitization or may be subjected to chemical sensitization.
  • chemical sensitization methods include conventional methods such as sulfur sensitization, reduction sensitization and gold sensitization. These methods may be used either alone or in combination.
  • Preferred chemical sensitization method is sulfur sensitization.
  • sulfur sensitizing agents which can be used include sulfur compounds contained in gelatin and various sulfur compounds such as thiosulfates, thioureas, thiozoles and rhodanines. Concrete examples thereof are those described in U.S. Patents 1,574,944, 2,278,947, 2,410,689, 2,728,668, 3,501,313 and 3,656,955.
  • Preferred sulfur compounds are thiosulfates and thiourea compounds.
  • pAg is preferably 8.3 or below, more preferably in the range of 7.3 to 8.0.
  • noble metal sensitization method is gold sensitization method using gold compounds, particularly gold complex salts.
  • gold compounds particularly gold complex salts.
  • other noble metal complex salts such as complex salts of platinum, palladium and iridium may be contained. Concrete examples thereof are described in U.S. Patent 2,448,060 and U.K. Patent 618,061.
  • reduction sensitizing agents examples include stannous salts, amines, formaminedisulfinic acid and silane compounds. Concrete examples of these compounds are described in U.S. Patents 2,487,850, 2,518,698, 2,983,609, 2,983,610 and 2,694,637.
  • Silver halide emulsion in the light-sensitive material used in the present invention may be composed of one kind of an emulsion or a combination of two or more kinds of emulsions (e.g., emulsions which are different in mean grain size, halogen composition or crystal habit or which are prepared under different chemical sensitization conditions).
  • chemical sensitization When chemical sensitization is conducted, it is particularly desirable that chemical sensitization is slightly conducted to such an extent that black pepper is not formed.
  • the term "slightly conducted” as used herein means that chemical sensitization time is shortened, temperature is lowered or the amount of the chemical sensitizing agent to be added is reduced in comparison with the chemical sensitization of the smaller-size grains.
  • the difference in terms of Alog E is 0.1 to 1.0, preferably 0.2 to 0.7 and it is preferred that the larger-size monodisperse emulsion has higher sensitivity.
  • the silver halide emulsion layer may be composed of a single layer or a multi-layer (e.g. two layers or three layers).
  • a multi-layer e.g. two layers or three layers.
  • different silver halide emulsions may be used, or the same emulsions may be used.
  • Gelatin can be advantageously used as a binder or protective colloid for photographic emulsions.
  • other hydrophilic colloid can be used.
  • examples of usable hydrophilic colloid include protein such as gelatin derivatives, gelatin-grafted polymers, albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose and cellulose sulfate; saccharide derivatives such as sodium alginate and starch derivatives; and various synthetic hydrophilic high-molecular materials such as homopolymers, for example, polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole and polyvinyl pyrazole and copolymers thereof.
  • Examples of usable gelatin include lime-processed gelatin, acid-processed gelatin, gelatin hydrolyzate and enzymatic decomposate of gelatin.
  • Sensitizing dyes e.g., cyanine dyes or merocyanine dyes
  • cyanine dyes or merocyanine dyes having absorption maximum in the visible region as described in JP-A-55-52050 (pages 45-53) can be added in the present invention, whereby the emulsions can be spectral-sensitized to longer wavelength side than sensitivity region inherent in silver halide.
  • sensitizing dyes may be used either alone or in combination.
  • a combination of sensitizing dyes are often used for the purpose of supersensitization.
  • the emulsions may contain dyes which themselves do not have any spectral sensitization effect or substances which do substantially not absorb visible light, but exhibit supersensitization activity.
  • the light-sensitive materials used in the present invention may contain various compounds to prevent fogging from being caused during the course of the manufacturing, storage or processing of the light-sensitive materials or to stabilize photographic performance.
  • the compounds which are known as anti-fogging agents or stabilizers include azoles such as benzthiazolium salts, nitroindazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptotetrazoles, mercaptothiazoles, mercaptobenzthiazoles, mercaptothiazoles, aminotriazoles, benzthiazoles and nitrobenztriazoles; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes such as triazaindenes, tetraazaindenes (particularly, 4-hydroxy-substituted(1,3,3a,7)tetraazaindenes) and pantaazaindenes; and benzen
  • benztriazoles e.g., 5-methyl-benztriazole
  • nitroindazoles e.g., 5-nitroindazole
  • These compounds may be contained in processing solutions. Further, compounds which release an inhibitor during development as described in JP-A-62-30243 may be contained as stabilizers or to inhibit black pepper from being formed.
  • the photographic materials used in the present invention may contain developing agents such as hydroquinone derivatives and phenidone derivatives for the purpose of using them as stabilizers, accelerators, etc.
  • the photographic emulsion layers and other hydrophilic colloid layers of the photographic materials used in the present invention may contain inorganic or organic hardening agents.
  • the hardening agents include chromium salts (e.g., chromium alum, chromium acetate), aldehydes (e.g., formaldehyde, glutaraldehyde), N-methylol compounds (e.g., dimethylol urea), dioxane derivatives, active vinyl compounds (e.g., 1,3,5-triacrylol-hexahydro-s-triazine, 1,3-vinylsulfonyl-2-propanol), active halogen compounds (e.g., 2,4-dichloro-6-hydroxy-s-triazine) and mucohalogenic acids (e.g., mucochloric acid). These compounds may be used either alone or in combination.
  • the photographic emulsion layers and other hydrophilic colloid layers of the photographic materials used in the present invention may contain various surfactants as coating aid or for the purpose of imparting antistatic properties, improving slipperiness or emulsifying dispersion, preventing sticking from being caused or improving photographic characteristics (e.g., development acceleration, high contrast, sensitization).
  • various surfactants as coating aid or for the purpose of imparting antistatic properties, improving slipperiness or emulsifying dispersion, preventing sticking from being caused or improving photographic characteristics (e.g., development acceleration, high contrast, sensitization).
  • surfactants examples include nonionic surfactants such as saponin (steroid), alkylene oxide derivatives (e.g., polyethylene glycol, polyethylene glycol/polypropylene glycol condensate, polyethylene glycol alkyl ethers, polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkylamines or amides and polyethylene oxide adducts of silicone), glycidol derivatives (e.g., alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides) and alkyl esters such as fatty acid esters of polyhydric alcohols; anionic surfactants having an acid group such as carboxy group, sulfo group, phospho group, sulfuric ester group or phosphoric ester group such as salts of alkylcarboxylic acids, salts of alkylsulfonic acids, salts of alkylbenzen
  • Surfactants which can be preferably used in the present invention are polyalkylene oxides having a molecular weight of not less than 600 described in JP-B-58-9412 (the term "JP-B” as used herein means an "examined Japanese patent publication").
  • fluorine-containing surfactants described in JP-A-60-80849 are used for the purpose of imparting antistatic properties.
  • the photographic emulsion layers and other hydrophilic colloid layers of the photographic materials used in the present invention may contain hydroquinone derivatives (called DIR-hydroquinone) which release a development restrainer according to the density of image during development.
  • DIR-hydroquinone hydroquinone derivatives
  • hydroquinone derivatives examples include compounds described in U.S. Patents 3,379,529, 3,620,746 4,377,634 and 4,332,878, JP-A-49-129536, JP-A-54-67419, JP-A-56-153336, JP-A-56-153342, JP-A-59-278853, JP-A-59-90435, JP-A-59-90436 and JP-A-59-138808.
  • the photographic emulsion layers and other hydrophilic colloid layers of the photographic materials used in the present invention may contain matting agents such as silica, magnesium oxide and polymethyl methacrylate to prevent sticking from being caused.
  • the photographic materials used in the present invention may contain a dispersion of a water-insoluble or difficultly soluble synthetic polymer for the purpose of dimensional stabilization.
  • the polymer include polymers of one or more monomers of alkyl (meth)acrylates, alkoxyacryl (meth)acrylates or glycidyl (meth)acrylates, and polymers of one or more monomer components thereof with acrylic acid or methacrylic acid.
  • the silver halide emulsion layers and other layers of the photographic materials used in the present invention contain compounds having an acid radical.
  • the compounds having an acid radical include organic acids such as salicylic acid, acetic acid and ascorbic acid and polymers and copolymers having a repeating unit derived from an acid monomer such as acrylic acid, maleic acid and phthalic acid. These compounds are described in the specifications of JP-A-61-223834, JP-A-61-228437, JP-A-62-25745 and JP-A-62-55642.
  • the particularly preferred low-molecular compound is ascorbic acid and the particularly preferred high-molecular compounds are water-dispersible latexes of copolymers of an acid monomer such as acrylic acid with a crosslinking monomer having at least two unsaturated groups such as divinylbenzene.
  • the above-described silver halide emulsions are coated on an appropriate support such as glass, a plastic film (e.g., cellulose acetate film or polyethylene terephthalate film), paper, baryta paper or polyolefin-coated paper. Among them, plastic films are preferred.
  • Development accelerators or nucleating infectious development accelerators suitable for use in the present invention include compounds described in JP-A-53-77616, JP-A-54-37732, JP-A-53-137133, JP-A-60-140340, and JP-A-60-14959. In addition thereto, compounds containing N or S atom are effective.
  • accelerators examples include the following compounds. n-C 4 H 9 N(C 2 H 4 OH) 2
  • the optimum amounts of these accelerators to be added vary depending on the types of the compounds, but they are used in an amount of generally 1.0 ⁇ 10 -3 to 0.5 g/m 2 , preferably 5.0 ⁇ 10 -3 to 0.1 g/m 2 .
  • These accelerators are dissolved in an appropriate solvent (e.g., H 2 O, an alcohol such as methanol or ethanol, acetone, dimethylformamide, methyl cellosolve) and then added to the coating solution.
  • an appropriate solvent e.g., H 2 O, an alcohol such as methanol or ethanol, acetone, dimethylformamide, methyl cellosolve
  • additives may be used in combination of two or more kinds of them.
  • Stable developing solutions can be used to obtain ultra-high-contrast photographic characteristics by using the silver halide light-sensitive materials without necessity of the use of conventional infectious developing solutions or high-alkali developing solutions having a pH of nearly 13 described in U.S. Patent 2,419,975.
  • the phenols having an acid dissociation constant of 1 ⁇ 10 -11 to 3 ⁇ 10 -13 which are used in the developing solutions include the following compounds.
  • R 5 , R 6 , R 7 and R 8 may be the same or different groups and each is hydrogen atom, amino group, carboxyl group, sulfo group, an alkyl group having 1 to 4 carbon atoms (which may be substituted) or an alkoxy group (which may be substituted).
  • Examples of the compounds represented by general formula (IV) include the following compounds.
  • the compound of IV-11 is particularly preferred.
  • the following compounds can be used for the developing solutions without particular limitations except that the developing solutions contain the above phenol compounds in an amount of at least 0.05 mol/l.
  • the developing solutions contain dihydroxybenzenes.
  • dihydroxybenzenes with 1-phenyl-3-pyrazolidones or combinations of dihydroxybenzenes with p-aminophenols are optionally used.
  • dihydroxybenzene developing agents used in the present invention include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,3-dibromohydroquinone and 2,5-dimethylhydroquinone.
  • hydroquinone is particularly preferred.
  • Examples of 1-phenyl-3-pyrazolidone or derivatives thereof which can be used as developing agents in the present invention include 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1-p-aminophenyl-4,4-dimethyl-3-pyrazolidone, 1-p-tolyl-4,4-dimethyl-3-pyrazolidone and 1-p-tolyl-4-methyl-4-hydroxymethyl-3-pyrazolidone.
  • the p-aminophenol developing agents which can be used in the present invention include N-methyl-p-aminophenol, p-aminophenol, N-( ⁇ -hydroxyethyl)-p-aminophenol, N-(4-hydroxyphenyl)glycine, 2-methyl-p-aminophenol and p-benzylaminophenol. Among them, N-methyl-p-aminophenol is preferred.
  • the developing agents are generally used in an amount of preferably 0.05 to 0.8 mol/l.
  • the former is used in an amount of 0.05 to 0.5 mol/l and the latter is used in an amount of not more than 0.06 mol/l.
  • Sulfites used as preservatives in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite and formaldehyde sodium bisulfite.
  • the sulfites are used in an amount of preferably at least 0.3 mol/l, particularly preferably at least 0.4 mol/l. It is desirable that the upper limit is 2.5 mol/l, particularly 1.2 mol/l.
  • Alkali agents used for setting pH include pH adjustors and buffering agents such as sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate.
  • additives which may be used in addition to the above-described components include compounds such as boric acid and borax, development restrainers such as sodium bromide, potassium bromide and potassium iodide; organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve, hexylene glycol, ethanol and methanol; and anti-fogging agents or black pepper inhibitors such as mercapto compounds (e.g., 1-phenyl-5-mercaptotetrazole and sodium 2-mercaptobenzimidazole-5-sulfonate), indazole compounds (e.g., 5-nitroindazole) and benztriazole compounds (e.g., 5-methylbenztriazole).
  • compounds such as boric acid and borax, development restrainers such as sodium bromide, potassium bromide and potassium iodide
  • organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide,
  • toning agents may be optionally contained.
  • the developing solutions used in the present invention may contain compounds as silver stain inhibitors described in JP-A-56-24347, compounds as development blurs inhibitors described in JP-A-62-212651 and compounds as dissolution aids described in JP-A-61-267759.
  • the developing solutions used in the present invention contain, as buffering agents, boric acids described in JP-A-62-186259 and saccharide (e.g., saccharose), oximes (e.g., acetoxime) and phenols (e.g., 5-sulfosalicylic acid) described in JP-A-60-93433.
  • saccharide e.g., saccharose
  • oximes e.g., acetoxime
  • phenols e.g., 5-sulfosalicylic acid
  • Fixing solutions are acidic aqueous solutions containing water-soluble aluminum compounds as hardening agents in addition to fixing agents and optionally acetic acid and dibasic acids (e.g., tartaric acid, citric acid or a salt thereof) and having a pH of not lower than 3.8, more preferably 4.0 to 5.5.
  • acetic acid and dibasic acids e.g., tartaric acid, citric acid or a salt thereof
  • the fixing agents include sodium thiosulfate and ammonium thiosulfate. Ammonium thiosulfate is particularly preferred from the viewpoint of the rate of fixing.
  • the amounts of the fixing agents to be used can be properly changed and are generally in the range of 0.1 to 5 mol/l.
  • the water-soluble aluminum salts which function mainly as hardening agents in the fixing solutions are compounds which are known as hardening agents for acid hardening fixers. Examples thereof include aluminum chloride, aluminum sulfate and potassium alum.
  • the water-soluble aluminum salts are used in an amount of 0.005 mol/l to 0.1 mol/l, preferably 0.01 mol/l to 0.07 mol/l.
  • dibasic acids tartaric acid or derivatives thereof and citric acid or derivatives thereof singly or in combination of two or more can be used.
  • the effective amounts of these compounds are at least 0.005 mol per liter of the fixing solution, and an amount of 0.01 mol/l to 0.03 mol/l is particularly effective.
  • Concrete examples include tartaric acid, potassium tartrate, sodium tartrate, sodium potassium tartrate, ammonium tartrate and potassium ammonium tartrate.
  • citric acid or derivatives thereof which can be effectively used in the present invention include citric acid, sodium citrate and potassium citrate.
  • the fixing solutions may contain preservatives (e.g., sulfite, bisulfite), pH buffering agents (e.g., acetic acid, boric acid), pH adjustors (e.g., ammonia, sulfuric acid), image storage improvers (e.g., potassium iodide) and chelating agents.
  • preservatives e.g., sulfite, bisulfite
  • pH buffering agents e.g., acetic acid, boric acid
  • pH adjustors e.g., ammonia, sulfuric acid
  • image storage improvers e.g., potassium iodide
  • Fixing temperature and time are preferably 20°C to 50°C and 10 seconds to one minute as in development.
  • Rinsing water may contain mildew proofing agents (e.g., compounds described in Germicidal and Antifungal Chemistry , written by Horiguchi and JP-A-62-115154), rinsing accelerators (e.g., sulfite) and chelating agents.
  • mildew proofing agents e.g., compounds described in Germicidal and Antifungal Chemistry , written by Horiguchi and JP-A-62-115154
  • rinsing accelerators e.g., sulfite
  • Rinsing is carried out to remove nearly completely silver salt dissolved by fixing and is preferably conducted at 20°C to 50°C for 10 seconds to 3 minutes. Drying is carried out at 40°C to 100°C, and drying time varies properly depending on environmental conditions, but is generally 5 seconds to 3.5 minutes.
  • roller conveying type automatic processors are described in the specifications of U.S. Patents 3,025,779 and 3,545,971, and are herein referred to simply as roller conveying type processor.
  • the roller conveying type processor comprises four stages of development, fixing, rinsing and drying. It is most preferred that the method of the present invention follows these four stages, though other stages (e.g., stop stage) is not removed.
  • the replenishment rate of rinsing water may be not more than 1200 ml/m 2 (including 0).
  • the description "the case where the replenishment rate of rinsing water (or stabilizing solution) is 0" means a rinsing method by means of called a standing water rinse system.
  • Multi-stage countercurrent systems e.g., two-stage, three-stage
  • Multi-stage countercurrent systems are known for a long time as a means for reducing replenishment rate.
  • Good processing performance can be obtained by combining the following techniques to solve problems which are caused by the less replenishment rate of rinsing water.
  • Rinsing bath or stabilizing bath may contain, as microbiocides, isothiazoline compounds described in R.T. Kreiman, J. Imaging Tech., Vol. 10, No. 6, 242 (1984), isothiazoline compounds described in Research Disclosure (RD), Vol. 205, No. 20526 (May 1981) and ibid., Vol. 228, No. 22845 (April 1983) and compounds described in JP-A-61-115154 and JP-A-62-209532.
  • the rinsing bath or the stabilizing bath may contain compounds described in Germicidal and Antifungal Chemistry , written by Hiroshi Horiguchi (Sankyo Shuppan 1982), Microcial Antifungal Technical Handbook, edited by Nippon Microcidal Antifungal Society (Hakuhodo 1986) and L.E. West Water Quality Criteria, Photo. Sci. & Eng., Vol. 9, No. 6 (1965), M.W. Beach, Microbiological Growths in Motion Picture Processing , SMPTE Journal Vol. 85 (1976), R.O. Deegan Photo Processing Wash Water Biocides, J. Imaging Tech., Vol. 10, No. 6 (1984).
  • a part or the whole of overflow solution from the rinsing bath or the stabilizing bath can be utilized as a processing solution having an ability of fixing which is used in the processing stage prior to the rinsing or stabilizing stage as described in JP-A-60-235133 and JP-A-63-129343, said overflow solution being formed by replenishing water provided with an antifungal means corresponding to the rate of processing in the rinsing or stabilizing bath used according to the present invention.
  • water-soluble surfactants or anti-foaming agents may be added to prevent treating agent components deposited on the squeezing rollers from being transferred to films and/or to prevent unevenness in foams which is liable to be caused when rinsing is carried out with a small amount of rinsing water.
  • Dye adsorbents described in JP-A-63-163456 may be used in the rinsing tank to prevent the light-sensitive materials from being stained by dyes dissolved out from the light-sensitive materials.
  • the developing solutions used in the present invention are kept in packaging materials having low oxygen permeability and low moisture permeability described in JP-A-61-73147.
  • Replenishment system described in JP-A-62-91939 can be preferably used for the developing solutions used in the present invention.
  • the silver halide photographic materials used in the present invention give high Dmax. Hence, when they are subjected to reduction treatment after image formation, high density can be kept even when dot area is reduced.
  • reducers containing, as oxidizing agent e.g. permanganate, persulfate, ferric salt, cupric salt, ceric salt, red prussiate or dichromate, singly or in combination and optionally inorganic acids such as sulfuric acid and alcohols and reducers containing oxidizing agents such as red prussiate and ethylenediaminetetraacetic acid iron(III) salt, silver halide solvent, such as thiosulfate, rhodanate, thiourea or their derivatives and optionally inorganic acids such as sulfuric acid.
  • oxidizing agent e.g. permanganate, persulfate, ferric salt, cupric salt, ceric salt, red prussiate or dichromate
  • inorganic acids such as sulfuric acid and alcohols
  • reducers containing oxidizing agents such as red prussiate and ethylenediaminetetraacetic acid iron(III) salt
  • silver halide solvent such as
  • Typical examples of the reducers which can be used in the present invention include Farmer's reducer, ethylenediaminetetraacetic acid iron(III) salt, potassium permanganate, ammonium persulfate reducer (Kodak R-5) and ceric salt reducer.
  • reduction processing is completed generally at a temperature of 10°C to 40°C, preferably 15°C to 30°C in a period of several seconds to several tens of minutes, particularly several minutes.
  • sufficiently wide reduction margin can be obtained under the above-described conditions.
  • the reducer is allowed to act on silver image formed in the emulsion layer through the upper light-insensitive layer containing the compound used in the present invention.
  • the methods include a method wherein the light-sensitive material for plate making is immersed in the reducer and the liquid is stirred and a method wherein the reducer is applied to the surface of the light-sensitive material for plate making by means of brush or roller.
  • Preferred embodiments of the present invention are as follows.
  • Figure 1 shows an embodiment during exposure when superimposed letter image is formed by overlay contact work wherein each sign represents the following member.
  • the temperature thereof was kept at 50°C, and 5,5'-dichloro-9-ethyl-3,3'-bis(3-sulfopropyl)oxacarbocyanine as a sensitizing dye and 10 -3 mol of a KI solution per mol of silver were added thereto. After a lapse of 15 minutes, the temperature was lowered.
  • the emulsion was re-dissolved and the following hydrazine derivative was added thereto at 40°C.
  • the compound of general formula (I) was added as indicated in Table 1. Further, 5-methylbenztriazole, 4-hydroxy-1,3,3a,7-tetraazaindene, the following compounds (a) and (b), 30 wt% (based on the weight of gelatin) of polyethyl acrylate and the following compound (c) as a hardening agent for gelatin were added thereto.
  • the resulting emulsion was coated on polyethylene terephthalate film (150 ⁇ m) having an undercoat layer (0.5 ⁇ m) composed of a vinylidene chloride copolymer in such an amount as to give a coating weight of 3.4 g/m 2 in terms of silver.
  • a protective layer comprising gelatin (1.5 g/m 2 ) and polymethyl methacrylate particles (average particle size: 2.5 ⁇ m, 0.3 g/m 2 ) was coated thereon by using the following surfactants.
  • the resulting samples were exposed to tungsten light (3200°K) through an optical wedge and 150 line contact screen.
  • the exposed samples were developed with the following developing solutions A and B at 38°C for 20 seconds, fixed with the following fixing solutions A and B, washed with water and dried by using an automatic processor FG680A (manufactured by Fuji Photo Film Co., Ltd.).
  • FG680A manufactured by Fuji Photo Film Co., Ltd.
  • 100 sheets of 20 ⁇ 24 inch films (50.8 cm ⁇ 61.0 cm) an area of which should be blackened to an extent of 50%, were processed with a replenishment rate of 100 ml per sheet of each of the developing solution and the fixing solution.
  • the results are shown in Table 1.
  • Fixing Solution A Fixing Solution B Ammonium thiosulfate 160.0 g 160.0 g Sodium thiosulfate 30.0 g 30.0 g Sodium sulfite 22.0 g 22.0 g Disodium ethylenediaminetetraacetate 0.1 g 0.1 g Tartaric acid 3.0 g 3.0 g Ammonia water (27%) 10.0 g 10.0 g Acetic acid (90%) 30.0 g 30.0 g Aluminum sulfate (27%) 35.0 g - Add water to make 1 liter pH was adjusted to 4.8 by sodium hydroxide.
  • sensitivity of 100 The reciprocal of exposure amount giving a blacking density of 1.5 when the film No. 1 was processed with the developing solution A and the fixing solution B, was referred to as sensitivity of 100.
  • the sensitivity in terms of the relative sensitivity is shown.
  • Halftone gradation (Logarithm of exposure amount giving dot percent of 95%) - (Logarithum of exposure amount giving dot percent of 5%)
  • Halftone dot quality was visually evaluated by five ranks. In five rank evaluation, a rank of 5 indicates the best quality and a rank of 1 indicates the worst quality. As the halftone original plate, the ranks of 5 and 4 indicate a quality which is practically usable, the rank of 3 indicates a quality which is practically usable limit level and the ranks of 2 and 1 indicate a quality which is practically unusable.
  • Drying characteristics were evaluated by the dryness of films when two sheets of films were put upon each other immediately after the completion of development, fixing, rinsing and drying in the automatic processor as mentioned above.
  • the mark ⁇ of drying characteristics means that the water contents of the films are high, and films have poor slipperiness and are hard to handle.
  • the mark ⁇ of drying characteristics means that the films have a lower water content and good slipperiness and are easy to handle.
  • the films containing the compounds of general formula (I) have long halftone gradation and wide tone reproduction exposure range and give good halftone dot quality.
  • the films are processed with the developing solution containing the compound IV-11 such as the developing solution A, a lowering in sensitivity is not caused after processing 100 sheets of the films.
  • the films are processed with the fixing solution containing the water-soluble aluminum such as the fixing solution A, drying characteristics are good.
  • the processing method which give long halftone gradation and good halftone dot quality, does not cause a change in sensitivity even after film processing and gives good drying characteristics by processing the silver halide light-sensitive materials containing a hydrazine nucleating agent and the redox compounds of e.g. general formula (I) with the developing solution containing the compound of e.g. general formula IV and then processing it with an acid hardening fixer containing the water-soluble aluminum compound.
  • aqueous solution of silver nitrate and an aqueous solution of sodium chloride were simultaneously mixed with an aqueous gelatin solution kept at 50°C in the presence of 5.0 ⁇ 10 -6 mol of (NH 4 ) 3 RhCl 6 per mol of silver.
  • soluble salts were removed by a method well known by those skilled in the art, gelatin was added thereto, and 2-methyl-4-hydroxy-1,3,3a,7-tetraazaindene as a stabilizer was then added thereto without carrying out chemical ripening.
  • the resulting emulsion was a cubic system monodisperse emulsion having a mean grain size of 0.15 ⁇ m.
  • the compound used in the present invention indicated in Table 2 was added, 30 wt% (on a solid basis; based on the weight of gelatin) of polyethyl acrylate latex was added and 1,3-vinylsulfonyl-2-propanol as a hardening agent was added thereto.
  • the resulting emulsion was coated on a polyester support in such an amount as to give a coating weight of 3.8 g/m 2 in terms of Ag.
  • the coating weight of gelatin was 1.8 g/m 2 .
  • a protective layer comprising gelatin (1.5 g/m 2 ), polymethyl methacrylate particles having an average particle size of 2.5 ⁇ m (0.3 g/m 2 ) as a matting agent, the following surfactants as coating aids, the following stabilizer and the following ultraviolet light-absorbing dye was coated thereon and dried.
  • Stabilizer Thioctic acid 2.1 mg/m 2
  • the samples were subjected to imagewise exposure through the original as shown in Fig. 1 by using a daylight printer p-607 (manufactured by Dainippon Screen KK).
  • the exposed samples were developed with the developing solutions A and B at 38°C for 20 seconds, fixed with the fixing solutions A and B, washed with water and dried by using the automatic processor FG680A (manufactured by Fuji Photo Film Co., Ltd.), said developing solutions A and B and said fixing solutions being the same as those used in Example 1.
  • 100 sheets of 20 ⁇ 24 inch films an area of which should be blackened to an extent of 50% were processed with a replenishment rate of 80 ml per sheet of each of the developing solution and the fixing solution.
  • the results are shown in Table 2.
  • a rank of superimposed letter image quality 5 means an image quality which shows the reproduction of 30 ⁇ m wide letter when exposure is properly carried out so that 50% dot area becomes 50% dot area in the light-sensitive material for dot to dot work with using the original as shown in Fig. 1, and the rank of 5 is very good superimposed letter image quality.
  • a rank of superimposed letter image quality 1 means an image quality which shows only the reproduction of letters of 150 ⁇ m wide or above when the same proper exposure is conducted, and the rank of 1 is bad superimposed letter image quality.
  • the ranks of 4 to 2 are set between the superimposed letter image quality 5 and the superimposed letter image quality 1 by organoleptic evaluation. The rank 3 or higher is practically usable level.
  • the films containing the compounds of general formula (I) provide good superimposed letter image quality.
  • the films are processed with the developing solution containing the compound IV-11 such as the developing solution A, a lowering in sensitivity is not caused after processing 100 sheets of the films.
  • the films are processed with the fixing solution containing the water-soluble aluminum such as the fixing solution A, drying characteristics are good.
  • the processing method which provides good superimposed letter image quality, does not cause a change in sensitivity even after film processing and gives good drying characteristics by processing the silver halide light-sensitive materials containing a hydrazine nucleating agent and the redox compounds of e.g. general formula (I) with the developing solution containing the compound of e.g. general formula IV and then processing it with an acid hardening fixer containing the water-soluble aluminum compound.
  • the method for processing stably and rapidly the silver halide photographic materials having excellent original reproducibility in the photographing of the letter original and the halftone original is made possible by the present invention.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
EP90909370A 1989-06-16 1990-06-15 Method of treating silver halide photographic material Expired - Lifetime EP0436027B1 (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
JP15406089 1989-06-16
JP154060/89 1989-06-16
JP18904089A JPH0387735A (ja) 1989-06-16 1989-07-21 ハロゲン化銀写真感光材料の処理方法
JP189040/89 1989-07-21
PCT/JP1990/000787 WO1990016015A1 (en) 1989-06-16 1990-06-15 Method of treating silver halide photographic material

Publications (3)

Publication Number Publication Date
EP0436027A1 EP0436027A1 (en) 1991-07-10
EP0436027A4 EP0436027A4 (en) 1991-11-27
EP0436027B1 true EP0436027B1 (en) 1998-10-14

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EP (1) EP0436027B1 (ja)
DE (1) DE69032701T2 (ja)
WO (1) WO1990016015A1 (ja)

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Publication number Priority date Publication date Assignee Title
DE69405535T2 (de) * 1994-03-11 1998-04-02 Agfa Gevaert Nv Photographisches Material, das einen neuen Typ eines Hydrazides enthält

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Publication number Priority date Publication date Assignee Title
ZA802893B (en) * 1979-05-16 1981-05-27 Ciba Geigy Hardening fixing belts for processing photographic materials
JPS6093433A (ja) * 1983-10-27 1985-05-25 Fuji Photo Film Co Ltd 現像方法
JPS60136741A (ja) * 1983-12-26 1985-07-20 Fuji Photo Film Co Ltd 写真感光材料の処理方法
JPH0690486B2 (ja) * 1985-03-19 1994-11-14 富士写真フイルム株式会社 ハロゲン化銀写真感光材料
JPS62235947A (ja) * 1986-04-07 1987-10-16 Fuji Photo Film Co Ltd 画像形成方法
JPS62235939A (ja) * 1986-04-07 1987-10-16 Fuji Photo Film Co Ltd ハロゲン化銀写真感光材料
US4684604A (en) * 1986-04-24 1987-08-04 Eastman Kodak Company Oxidative release of photographically useful groups from hydrazide compounds

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DE69032701T2 (de) 1999-03-11
EP0436027A1 (en) 1991-07-10
WO1990016015A1 (en) 1990-12-27
DE69032701D1 (de) 1998-11-19
EP0436027A4 (en) 1991-11-27

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