EP0628861B1 - Photographisches Silberhalogenidmaterial - Google Patents

Photographisches Silberhalogenidmaterial Download PDF

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Publication number
EP0628861B1
EP0628861B1 EP93109290A EP93109290A EP0628861B1 EP 0628861 B1 EP0628861 B1 EP 0628861B1 EP 93109290 A EP93109290 A EP 93109290A EP 93109290 A EP93109290 A EP 93109290A EP 0628861 B1 EP0628861 B1 EP 0628861B1
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EP
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Prior art keywords
group
silver halide
sensitive material
silver
compound
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EP93109290A
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English (en)
French (fr)
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EP0628861A1 (de
Inventor
Kazumi C/O Fuji Photo Film Co. Ltd. Nii
Toshihide C/O Fuji Photo Film Co. Ltd. Ezoe
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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Priority to DE69326886T priority Critical patent/DE69326886T2/de
Priority to EP93109290A priority patent/EP0628861B1/de
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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
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/061—Hydrazine compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
    • G03C2001/03517—Chloride content
    • 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
    • G03C2200/00—Details
    • G03C2200/38—Lippmann (fine grain) emulsion

Definitions

  • This invention relates to a silver halide photographic material and a method of forming a ultrahigh contrast negative image using the same. More particularly, it relates to a ultrahigh contrast negative silver halide photographic material suitable for use in photomechanical process.
  • an image formation system providing ultrahigh contrast (especially a gamma exceeding 10) is required for achieving satisfactory reproduction of a dot image having continuous tone or a line image.
  • hydrazine compounds non-diffusive for the purpose of minimizing adverse influences which may arise from the hydrazine compounds dissolved in a developing solution.
  • These non-diffusive hydrazine compounds should be used in large quantities for sufficient sensitization and improvement in contrast so that they are apt to cause deterioration of physical properties of the developed light-sensitive layers or to precipitate in a coating composition.
  • a light-sensitive material containing such a non-diffusive hydrazine compound fails to obtain sufficient high contrast when developed with a fatigued developing solution after use for processing a large volume of photographic materials.
  • a high contract system using the conventional hydrazine compound involves use of a developing solution having a relatively high pH, e.g., 12.0 or higher, which entails not only danger on handling but cost for waste liquid treatment due to high BOD or COD. Because a large amount of a pH buffer must be added to a developing solution for maintaining the pH constant, the developing solution is sticky due to the so increased solid content and is hardly wiped away when scattered.
  • EP-A-0 598 315 describes the use of hydrazine compounds in a silver halide photographic photosensitive material. These compounds comprise two quaternary ammonium groups. The photographic materials using such a compound may be developed at a low pH.
  • An object of the present invention is to provide a silver halide photographic material for photomechanical processing which exhibits excellent stability in development processing and can be rapidly processed, which can be developed at a reduced pH and, moreover, which has a small variation of D max .
  • a silver halide light-sensitive material comprising a support and a silver halide emulsion layer and containing a compound represented by formula (I): wherein L 1 represents a single bond, -O-, -S-, -NR 6 -, -CO-, SO 2 -, -P(O)(G 2 R 6 )- or a combination thereof; L 2 represents -SO 2 NR 6 -, -NR 6 SO 2 NR 6 -, -CONR 6 -, -NR 6 CONR 6 - or -G 2 P(O)(G 2 R 6 )NR 6 -; G 1 represents -CO-, -SO 2 -, -SO-, -COCO-, a thiocarbonyl group, an iminomethylene group or -P(O)(G 2 R 6 )-; G 2 represents a single bond, -O- or -NR 6 -; R 1 represents an aliphatic
  • the aliphatic group as represented by R 1 preferably includes those having from 1 to 30 carbon atoms, and particularly a straight chain, branched or cyclic alkyl group having from 1 to 20 carbon atoms.
  • the aromatic group as represented by R 1 includes a monocyclic or bicyclic aryl group, or an unsaturated heterocyclic group which includes, for example, 5- or 6-membered rings containing at least one of N, S, and 0 and which may be condensed with an aryl group.
  • the aliphatic group or aromatic group for R 1 may be substituted typically with an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, a substituted amino group, a ureido group, a urethane group, a mercapto group, an aryloxy group, a sulfamoyl group, a carbamoyl group, an alkyl or arylthio group, an alkyl or arylsulfonyl group, an alkyl or arylsulfinyl group, a hydroxyl group, a halogen atom, a cyano group, a sulfo group, an aryloxycarbonyl group, an acyl group, an alkoxycarbonyl group, an acyloxy group, a carbonamido group, a sulfonamido group, a carboxyl group,
  • substituents are an alkyl group (preferably having 1 to 20 carbon atoms), an aralkyl group (preferably having 7 to 30 carbon atoms), an alkoxy group (preferably having 1 to 20 carbon atoms), a substituted amino group (preferably an amino group substituted with an alkyl group having 1 to 20 carbon atoms), an acylamino group (preferably having 2 to 30 carbon atoms), a sulfonamido group (preferably having 1 to 30 carbon atoms), a ureido group (preferably having 1 to 30 carbon exams), and a phosphoric acid amido group (preferably having 1 to 30 carbon atoms). These substituents may further be substituted.
  • the three R 1 's in formula (I) may be the same or different, or they may be linked together to form a ring.
  • the divalent aliphatic group as represented by R 2 , R 3 or R 4 preferably include those containing from 1 to 30 carbon atoms, and more preferably a straight chain, branched or cyclic alkylene group having from 1 to 20 carbon atoms.
  • the divalent aromatic group as represented by R 2 , R 3 or R 4 includes a monocyclic or bicyclic arylene group or an unsaturated divalent heterocyclic group which may be condensed with an aryl group.
  • R 2 preferably represents an alkylene group having from 1 to 10 carbon atoms
  • R 3 and R 4 each preferably represent an arylene group, particularly a benzene ring-containing arylene group.
  • R 2 , R 3 or R 4 may be substituted.
  • Typical substituents include those enumerated above as substituents for R 1 .
  • L 1 represents a single bond, -O-, -S-, -NR 6 -, -CO-, SO 2 -, -P(O)(G 2 R 6 )- or a combination thereof, preferably -SO 2 NR 6 -, -NR 6 SO 2 NR 6 -, -CONR 6 -, -NR 6 CONR 6 - or -G 2 P(O)(G 2 R 6 )NR 6 -, and more preferably -CONR 6 -.
  • L 2 preferably represents -SO 2 NR 6 -.
  • n 0 or 1, and preferably 1.
  • the aliphatic group as represented by R 5 is preferably an alkyl group having from 1 to 4 carbon atoms, and the aromatic group as represented by R 5 is preferably a monocyclic or bicyclic aryl group, e.g., a benzene ring-containing group.
  • R 5 preferably represents a hydrogen atom, an alkyl group (e.g., methyl, trifluoromethyl, 3-hydroxypropyl, 3-methanesulfonamidopropyl or phenylsulfonylmethyl), an aralkyl group (e.g., o-hydroxybenzyl), an aryl group (e.g., phenyl, 3,5-dichlorophenyl, o-methanesulfonamidophenyl, 4-methanesulfonylphenyl or 2-hydroxymethylphenyl), etc., with a hydrogen atom being particularly preferred.
  • an alkyl group e.g., methyl, trifluoromethyl, 3-hydroxypropyl, 3-methanesulfonamidopropyl or phenylsulfonylmethyl
  • an aralkyl group e.g., o-hydroxybenzyl
  • an aryl group e.g., pheny
  • R 5 may be substituted with, for example the substituents mentioned above for R 1 .
  • G 1 is most preferably -CO-.
  • R 5 may be a group which makes the G 1 -R 5 moiety be split off the rest of the molecule and induces a cyclization reaction to form a cyclic structure including the -G 1 -R 5 moiety. Specific examples of such a group are described, e.g., in JP-A-63-29751 (the term "JP-A" as used herein means an "unexamined published Japanese patent application").
  • R 6 preferably represents a hydrogen atom or an alkyl group having from 1 to 6 carbon atoms, and most preferably a hydrogen atom. When there are two or more R 6, s or G 2 's per molecule, they may be the same or different.
  • R 1 , R 2 , R 3 , R 4 or R 5 in formula (I) may contain therein a ballast group or a polymer which are generally employed in immobile photographically useful additives, such as couplers.
  • the ballast group is an organic group which contains at least 8 carbon atoms and is relatively inert to photographic properties.
  • Usable ballast groups include an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, an phenoxy group, and an alkylphenoxy group.
  • the polymer which may be incorporated includes those described in JP-A-1-100530.
  • R 1 , R 2 , R 3 , R 4 or R 5 in formula (I) may further contain therein a group which accelerates adsorption onto silver halide grains.
  • Suitable adsorption accelerating groups include a thiourea group, a heterocyclic thioamido group, a heterocyclic mercapto group, a triazole group. Specific examples of these groups are described in U.S.
  • the hydrazine compound can be synthesized by utilizing the processes disclosed, e.g., in JP-A-61-213847, JP-A-62-260153, U.S. Patent 4,684,604, JP-A-1-269936, U.S. Patents 3,379,529, 3,620,746, 4,377,634, and 4,332,878, JP-A-49-129536, JP-A-56-153336, JP-A-56-153342, and U.S. Patents 4,988,604 and 4,994,365.
  • a typical synthesis example is given below.
  • the hydrazine compound (I) is used as dissolved in an appropriate water-miscible organic solvent, such as an alcohol (e.g., methyl alcohol, ethyl alcohol, propyl alcohol or a fluorinated alcohol), a ketone (e.g., acetone or methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide, methyl cellosolve, etc.
  • an alcohol e.g., methyl alcohol, ethyl alcohol, propyl alcohol or a fluorinated alcohol
  • ketone e.g., acetone or methyl ethyl ketone
  • dimethylformamide dimethyl sulfoxide
  • methyl cellosolve methyl cellosolve
  • the hydrazine compound (I) may also be used in the form of an emulsified dispersion prepared by a well-known dispersion method using an oil (e.g., dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate) and an auxiliary solvent (e.g., ethyl acetate or cyclohexanone). It is also possible to use the hydrazine compound (I) as a dispersion prepared by a well-known solid dispersion method in which a powdered compound is dispersed in water in a ball mill, a colloid mill, etc. or by ultrasonic waves.
  • an oil e.g., dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate
  • an auxiliary solvent e.g., ethyl acetate or cyclohexanone
  • the hydrazine compound (I) is preferably used in an amount ranging from 1.0 x 10 -6 to 5 x 10 -2 mole, and preferably from 1.0 x 10 -5 to 2 x 10 -2 mole, per mole of silver halide.
  • the compound (I) is preferably incorporated into a silver halide emulsion layer but may be incorporated into other light-insensitive hydrophilic colloidal layers, such as a protective layer, an intermediate layer, a filter layer or an antihalation layer. Where it is added to a silver halide emulsion layer, the addition may be effected at any arbitrary stage of from the start of chemical ripening and before coating.
  • the compound (I) is preferably added after completion of chemical ripening and before coating, and more preferably added to a coating composition to be coated.
  • the silver halide emulsion may have any halogen composition, such as silver chloride, silver chlorobromide, silver iodobromide, and silver iodochlorobromide.
  • halogen composition such as silver chloride, silver chlorobromide, silver iodobromide, and silver iodochlorobromide.
  • silver halide grains comprising at least 60 mol%, and particularly 75 ml% or more, of silver chloride are preferred.
  • silver halide grains comprising at least 70 mol%, and particularly 90 mol% or more, of silver bromide with a silver iodide content being not more than 10 mol%, and particularly from 0.1 to 5 mol%, are preferred.
  • Fine silver halide grains e.g., having a mean grain size of 0.7 ⁇ m or less
  • a particularly preferred mean grain size is 0.5 ⁇ m or less.
  • Grain size distribution is not essentially limited, but a mono-dispersion is preferred.
  • the terminology "mono-dispersion” as used herein means a dispersion in which at least 95% of the weight or number of grains fall within a size range of ⁇ 40% of a mean grain size.
  • Silver halide grains in a photographic emulsion may have a regular crystal form, such as a cubic form and an octahedral form, or an irregular crystal form, such as a spherical form and a plate-like form, or a composite form of these crystal forms. Cubic grains are particularly preferred.
  • Individual silver halide grains may have a uniform phase or different phases between the inside and the surface layer thereof. Two or more different silver halide emulsions separately prepared may be used as a mixture.
  • a cadmium salt, a sulfite salt, a lead salt, a thallium salt, a rhodium salt or a complex thereof, an iridium salt or a complex thereof, etc. may be present in the system.
  • Suitable rhodium salts include rhodium monochloride, rhodium dichloride, rhodium trichloride, ammonium hexachlororhodate and, for preference, water-soluble halogeno-complex compounds of trivalent rhodium, e.g., hexachlororhodic (III) acid or salts thereof (e.g., ammonium salt, sodium salt or potassium salt).
  • the water-soluble rhodium salt is usually added in an amount of from 1.0 x 10 -8 to 1.0 x 10 -3 mol, and preferably from 1.0 x 10 -7 to 5.0 x 10 -4 mol, per mol of silver halide.
  • the silver halide emulsion may or may not be chemically sensitized. Chemical sensitization of a silver halide emulsion is carried out by sulfur sensitization, reduction sensitization, noble metal sensitization, or combination thereof.
  • noble metal sensitization techniques typical is gold sensitization using a gold compound, usually a gold complex.
  • Sulfur sensitization is effected by using a sulfur compound contained in gelatin as well as various sulfur compounds, e.g., thiosulfates, thioureas, thiazoles, and rhodanines.
  • Reduction sensitization is carried out by using a reducing compound, e.g., stannous salts, amines, formamidinesulfinic acid, and silane compounds.
  • a reducing compound e.g., stannous salts, amines, formamidinesulfinic acid, and silane compounds.
  • the silver halide emulsion layers may further contain known spectral sensitizing dyes.
  • Useful sensitizing dyes, combination of dyes exhibiting supersensitization, and substances showing supersensitization are disclosed in Research Disclosure , Vol. 176, No. 17643, p. 23, IV-J (Dec., 1978).
  • Binders or protective colloids which can be used in the silver halide emulsions include gelatin to advantage.
  • Hydrophilic colloids other than gelatin may also be employable, including proteins, e.g., gelatin derivatives, graft polymers of gelatin and other high polymers, albumin, and casein; cellulose derivatives, e.g., hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfate; sugar derivatives, e.g., sodium alginate and starch derivatives; and a variety of synthetic hydrophilic high polymers, e.g., polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, and polyvinylpyrazole, as well as copolymers comprising monomers constituting these homopolymers.
  • proteins e.g., gelatin derivatives, graft poly
  • Gelatin to be used includes lime-processed gelatin, acid-processed gelatin, hydrolysis products of gelatin, and enzymatic decomposition products of gelatin.
  • various compounds can be introduced into the light-sensitive material.
  • Such compounds include azoles, such as benzothiazolium salts, nitroindazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, aminotriazoles, benzothiazoles, and nitrobenzotriazoles; mercaptopyrimidines; mercaptotriazines; thioketo compounds, such as oxazolinethione; azaindenes, such as triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a,7)-tetraazaindenes), and pentaazaindenes; hydroquinone and derivatives thereof; disulfides, such as thioctic acid; benzenethiosul
  • the light-sensitive materials may contain an organic desensitizer containing at least one water-soluble or alkali-dissociating group. Suitable organic desensitizers are illustrated in JP-A-63-64039.
  • the organic desensitizer is usually added to a silver halide emulsion layer in an amount of from 1.0 x 10 -8 to 1.0 x 10 -4 mol/m 2 , and preferably of from 1.0 x 10 -7 to 1.0 x 10 -5 mol/m 2 .
  • the light-sensitive materials may contain a development accelerator or a nucleation infectious development accelerator.
  • a development accelerator or a nucleation infectious development accelerator examples include JP-A-53-77616, JP-A-54-37732, JP-A-53-137133, JP-A-60-140340, and JP-A-60-14959 as well as various compounds containing a nitrogen or sulfur atom.
  • the development accelerator is used in an amount usually of from 1.0 x 10 -3 to 0.5 g/m 2 , and preferably from 5.0 x 10 -3 to 0.1 g/m 2 , although the optimum amount varies depending on the kind of the compound.
  • the development accelerator can be incorporated into a coating composition as dissolved in an appropriate solvent, e.g., water, alcohols (e.g., methyl alcohol and ethyl alcohol), acetone, dimethylformamide, and methyl cellosolve.
  • additives may be used either individually or in combination of two or more thereof.
  • the emulsion layers or other hydrophilic colloidal layers of the light-sensitive material may contain a water-soluble dye as a filter dye or an anti-irradiation dye or for various other purposes.
  • Filter dyes to be used include those for reducing photographic sensitivity, preferably ultraviolet absorbents having a spectral absorption maximum in the intrinsic sensitivity region of silver halide and those for improving safety against safelight in handling of light-sensitive materials for bright room, i.e., dyes showing substantial light absorption in the region chiefly in the range of from 310 to 600 nm.
  • these dyes are preferably added to an emulsion layer or fixed in a light-insensitive hydrophilic colloidal layer farther from a support than a silver halide emulsion layer by using a mordant.
  • the dyes are added in an amount usually of from 1 x 10 -3 to 1 g/m 2 , and preferably of from 10 to 500 mg/m 2 , though varying depending on the molar absorption coefficient of the dye.
  • the above-mentioned dyes are added to a coating composition for a light-sensitive and/or light-insensitive hydrophilic colloidal layer in the form of a solution in an appropriate solvent, e.g., water, an alcohol (e.g., methyl alcohol, ethyl alcohol, or propyl alcohol), acetone, methyl cellosolve or a mixture thereof.
  • an appropriate solvent e.g., water, an alcohol (e.g., methyl alcohol, ethyl alcohol, or propyl alcohol), acetone, methyl cellosolve or a mixture thereof.
  • These dyes may be used either individually or in combination of two or more thereof.
  • Patent 2,527,583, merocyanine dyes or oxonol dyes described in U.S. Patents 3,486,897, 3,652,284, and 3,718,472, enaminohemioxonol dyes described in U.S. Patent 3,976,661, and other dyes described in British Patents 584,609 and 1,177,429, JP-A-48-85130, JP-A-49-99620, JP-A-49-114420, and U.S. Patents 2,533,472, 3,148,187, 3,177,078, 3,247,127, 3,540,887, 3,575,704, and 3,653,905 may also be employed.
  • the silver halide emulsion layers or other hydrophilic colloidal layers may contain an organic or inorganic hardening agent, such as chromates (e.g., chromium alum and chromium acetate), aldehydes (e.g., formaldehyde, glyoxal, and glutaraldehyde), N-methylol compounds (e.g., dimethylolurea and methyloldimethylhydantoin), dioxane derivatives (e.g., 2,3-dihydroxydioxane), active vinyl compounds (e.g., 1,3,5-triacryloyl-hexahydro-s-triazine and 1,3-vinylsulfonyl-2-propanol), active halogen compounds (e.g., 2,4-dichloro-6-hydroxy-s-triazine), and mucohalogenic acids (e.g., mucochloric acid and mucophenoxychloric
  • the silver halide emulsion layers or other hydrophilic colloidal layers may further contain various surface active agents for the purpose of coating aid, static charge prevention, improvement of slip properties, emulsification and dispersion aid, prevention of blocking, and improvement of photographic characteristics (e.g., acceleration of development, increase of contrast, and increase of sensitivity).
  • various surface active agents for the purpose of coating aid, static charge prevention, improvement of slip properties, emulsification and dispersion aid, prevention of blocking, and improvement of photographic characteristics (e.g., acceleration of development, increase of contrast, and increase of sensitivity).
  • Useful surface active agents include nonionic surface active agents, such as saponin (steroid type), alkylene oxide derivatives (e.g., polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkylamines or amides, polyethylene oxide adducts of silicone), glycidol derivatives (e.g., alkenylsuccinic acid polyglycerides, and alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, and alkyl esters of saccharides; anionic surface active agents containing an acid radical, e.g., a carboxyl group, a sulfo group, a phospho group, a sulfuric ester group, and a phosphoric ester group, such as alkylcarboxylate
  • JP-B-58-9412 a polyalkylene oxide having a molecular weight of 600 or more as disclosed in JP-B-58-9412 (the term "JP-B” as used herein means an "examined published Japanese patent application”).
  • polymer latices such as polyalkyl acrylates, may be used.
  • the silver halide light-sensitive material can be processed with a stable developing solution to obtain ultrahigh contrast characteristics. There is no need to use conventional infectious developers or highly alkaline developers having a pH of nearly 13 as described in U.S. Patent 2,419,975.
  • a negative image having sufficiently high contrast can be obtained by processing the silver halide light-sensitive material with a developing solution containing 0.15 mol/l or more of a sulfite ion as a preservative and having a pH between 10.5 and 12.3, particularly between 11.0 and 12.0.
  • a developing agent which can be used in the developing solution is not particularly restricted.
  • dihydroxybenzenes e.g., hydroquinone
  • 3-pyrazolidones e.g., 1-phenyl-3-pyrazolidone and 4,4-dimethyl-1-phenyl-3-pyrazolidone
  • aminophenols e.g., N-methyl-p-aminophenol
  • a combination of a dihydroxybenzene as a main developing agent and a 3-pyrazolidone or an aminophenol as an auxiliary developing agent is particularly suitable for development of the light-sensitive material.
  • the dihydroxybenzene is preferably used in an amount of from 0.05 to 0.5 mol/l
  • the 3-pyrazolidone or aminophenol is preferably used in an amount of not more than 0.06 mol/l.
  • the developing solution may further contain a pH buffering agent (e.g., the compounds described in JP-A-60-93433 and JP-A-62-186259, a development inhabitor (e.g., a bromide and an iodide), and an organic antifoggant (nitroindazoles or benzotriazoles are particularly preferred).
  • a pH buffering agent e.g., the compounds described in JP-A-60-93433 and JP-A-62-186259
  • a development inhabitor e.g., a bromide and an iodide
  • an organic antifoggant nitroindazoles or benzotriazoles are particularly preferred.
  • the developing solution may furthermore contain a water softener, a dissolution aid (e.g., the compounds disclosed in JP-A-61-267759), a toning agents, a development accelerator, a surface active agent (the above-described polyalkylene oxides are particularly preferred), a defoaming agent, a hardening agent, a silver stain inhibitor (e.g., the compounds disclosed in JP-A-56-24347, e.g., 2-mercaptobenzimidazolesulfonic acids), and so on.
  • a water softener e.g., a dissolution aid (e.g., the compounds disclosed in JP-A-61-267759), a toning agents, a development accelerator, a surface active agent (the above-described polyalkylene oxides are particularly preferred), a defoaming agent, a hardening agent, a silver stain inhibitor (e.g., the compounds disclosed in JP-A-56-24347, e
  • a fixing solution which can be used for processing may have any known composition.
  • Usable fixing agents include thiosulfates, thiocyanates, and organic sulfur compounds known to be effective as a fixing agent.
  • the fixing solution may contain a water-soluble aluminum salt, etc. as a hardening agent.
  • the processing temperature usually ranges from 18° to 50°C.
  • Photographic processing of the light-sensitive material is desirably carried out by means of an automatic developing machine.
  • the light-sensitive material provides a negative image having sufficiently high contrast even when rapidly processed in an overall processing time (the time of from entering an automatic developing machine through withdrawal) of from 90 seconds to 120 seconds.
  • a silver nitrate aqueous solution and a sodium chloride aqueous solution were simultaneously added to a gelatin aqueous solution kept at 40°C in the presence of 5.0 x 10 -6 mol of NH 4 RhCl 6 per mol of silver. After soluble salts were removed by a well-known method, gelatin was added to the emulsion. To the primitive emulsion was added 2-methyl-4-hydroxy-1,3,3a,7-tetraazaindene as a stabilizer to obtain a mono-dispersed emulsion of cubic grains having a mean grain size of 0.2 ⁇ m.
  • a polyethyl acrylate latex in an amount of 30% (solid basis) based on gelatin and 1,3-divinylsulfonyl-2-propanol as a hardening agent.
  • the resulting coating composition was coated on a polyester film to a silver coverage of 3.8 g/m 2 (gelatin coverage: 1.8 g/m 2 ).
  • a composition comprising 1.5 g/m 2 of gelatin and 0.3 g/m 2 of polymethyl methacrylate particles having a particle size of 2.5 ⁇ m was coated on the silver halide emulsion layer to form a protective layer.
  • the resulting sample for dot-to-dot work was imagewise exposed to light through the original shown in Fig. 1 of JP-A-2-293736 using a bright room printer "P-627 FM" manufactured by Dainippon Screen Mfg. Co., Ltd., developed with Developing Solution A having the formulation shown below at 38°C for 20 seconds in an automatic developing machine "FG 710 NH” manufactured by Fuji Photo Film Co., Ltd., fixed with a fixing solution "GR-F 1" produced by Fuji Photo Film Co., Ltd., washed with water, and dried.
  • the light-sensitive material for dot-to-dot work was exposed under proper conditions so that a dot area of 50% of the original might be reproduced on the light-sensitive material as a dot area of 50%.
  • the image quality was rated "5" (best quality).
  • image quality was rated "1" (worst quality).
  • Image quality between "5" and "1” was dividedly rated "4", "3", and “2” by visual observation. Image quality levels rated "3" or higher are acceptable for practical use.
  • D max is a maximum density of the sample exposed in the same manner as described above.
  • Developing Solution A was put in the same automatic developing machine as used above, and the machine was run at 38°C for 8 hours a day without passing films. After 5-day running, the sample was processed with the thus air-fatigued developing solution, and the photographic properties of the processed sample were evaluated in the same manner as described above. The results obtained are shown in Table 2 below.
  • ⁇ D is a difference between the D max of Table 1 and that of Table 2. It is seen that the samples according to the present invention undergo less variation in D max .
  • a silver nitrate aqueous solution and a mixed aqueous solution of potassium iodide and potassium bromide were simultaneously added to a gelatin aqueous solution kept at 50°C for 60 minutes in the presence of 4 x 10 -7 mol/mol-Ag of potassium hexachloroiridate (III) and ammonia while maintaining a pAg at 7.8 to prepare a mono-dispersed emulsion of cubic silver halide grains having a mean grain size of 0.28 ⁇ m and an average silver iodide content of 0.3 mol%.
  • 40 g/mol-Ag of inert gelatin was added thereto.
  • 5,5'-Dichloropotassium iodide were added to the emulsion while maintaining at 50°C. After allowing the emulsion to stand for 15 minutes, the temperature was decreased.
  • a 150 ⁇ m-thick polyethylene terephthalate film having a 0.5 ⁇ m-thick subbing layer comprising a vinylidene chloride copolymer was coated with the coating composition to a silver coverage of 3.8 g/m 2 .
  • a coating composition having the following formulation was coated on the emulsion layer to form a protective layer.
  • Formulation of Developing Solution B Hydroquinone 50.0 g N-Methyl-p-aminophenol 0.3 g Sodium hydroxide 18.0 g Potassium hydroxide 20.0 g Potassium sulfite 30.0 g Disodium ethylenediaminetetraacetate 1.0 g Potassium bromide 10.0 g 5-Methylbenzotriazole 0.4 g 2-Mercaptobenzimidazole-5-sulfonic acid 0.3 g Sodium 3-(5-mercaptotetrazole)benzenesulfonate 0.2 g N-n-Butyldiethanolamine 7.0 g Sodium toluenesulfonate 8.0 g Water to make 1 l pH adjusted to 10.7
  • Dot quality was visually evaluated and rated “5" (best quality), "4" (acceptable for practical use), “3” (lowest limit for practical use), “2" (unacceptable for practical use), or "1" (worst quality).
  • D max is an optical density at an exposure amount (0.5 + log E 3 ) larger than the exposure amount providing a density of 1.5 (log E 3 ) by 0.5.

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Claims (13)

  1. Lichtempfindliches Silberhalogenidmaterial, umfassend einen Träger und eine Silberhalogenid-Emulsionsschicht und enthaltend eine Verbindung, dargestellt durch Formel (I) :
    Figure 00490001
    wobei L1 eine Einfachbindung, -O-, -S-, -NR6-, -CO-, SO2-, -P(O) (G2R6)- oder eine Kombination hiervon darstellt; L2 -SO2NR6-, -NR6SO2NR6-, -CONR6-, -NR6CONR6- oder -G2P(O) (G2R6)NR6- darstellt; G1 -CO-, -SO2-, -SO-, -COCO-, eine Thiocarbonylgruppe, eine Iminomethylengruppe oder -P(O) (G2R6)- darstellt; G2 eine Einfachbindung, -O- oder -NR6- darstellt; R1 eine aliphatische Gruppe oder eine aromatische Gruppe, die substituiert sein können, oder eine ungesättigte heterocyclische Gruppe darstellt, unter der Voraussetzung, dass R1 keine quaternäre Ammoniumgruppe umfasst; R2, R3 und R4 jeweils eine zweiwertige aliphatische Gruppe oder eine zweiwertige aromatische Gruppe, die substituiert sein können, darstellt; R5 ein Wasserstoffatom, eine aliphatische Gruppe, eine aromatische Gruppe, eine Alkoxygruppe, eine Aryloxygruppe oder eine Aminogruppe darstellt; R6 ein Wasserstoffatom, eine aliphatische Gruppe oder eine aromatische Gruppe darstellt; m 0 oder 1 darstellt; und X- ein Gegenanion oder ein Gegenanionteil eines intramolekularen Salzes darstellt, wobei die folgenden Verbindungen ausgeschlossen sind:
    Figure 00500001
    Figure 00500002
    Figure 00500003
  2. Lichtempfindliches Silberhalogenidmaterial gemäss Anspruch 1, wobei die aliphatische Gruppe für R1 eine Alkylgruppe mit 1 bis 20 Kohlenstoffatomen ist und die aromatische Gruppe für R1 eine monocyclische oder bicyclische Arylgruppe oder eine ungesättigte heterocyclische Gruppe ist.
  3. Lichtempfindliches Silberhalogenidmaterial gemäss Anspruch 1, wobei die zweiwertige aliphatische Gruppe für R2, R3 oder R4 eine Alkylengruppe mit 1 bis 20 Kohlenstoffatomen ist, und die zweiwertige aromatische Gruppe für R2, R3 oder R4 eine monocyclische oder bicyclische Arylengruppe oder eine ungesättigte zweiwertige heterocyclische Gruppe ist.
  4. Lichtempfindliches Silberhalogenidmaterial gemäss Anspruch 1, wobei L1 -SO2NR6-, -NR6SO2NR6-, -CONR6-, -NR6CONR6- oder -G2(P)O(G2R6)NR6- darstellt.
  5. Lichtempfindliches Silberhalogenidmaterial gemäss Anspruch 1, wobei die aliphatische Gruppe für R5 eine Alkylgruppe mit 1 bis 4 Kohlenstoffatomen ist und die aromatische Gruppe für R5 eine monocyclische oder bicyclische Arylgruppe ist.
  6. Lichtempfindliches Silberhalogenidmaterial gemäss Anspruch 1, wobei G1 -CO- darstellt.
  7. Lichtempfindliches Silberhalogenidmaterial gemäss Anspruch 1, wobei die Verbindung von Formel (I) in einer Menge von 1,0 x 10-6 bis 5 x 10-2 mol/mol Silberhalogenid enthalten ist.
  8. Lichtempfindliches Silberhalogenidmaterial gemäss Anspruch 7, in dem die Verbindung der Formel (I) in einer Menge von 1,0 x 10-5 bis 2 x 10-2 mol/mol Silberhalogenid enthalten ist.
  9. Lichtempfindliches Silberhalogenidmaterial gemäss Anspruch 1, in dem die Verbindung der Formel (I) in der Silberhalogenid-Emulsionsschicht eingebaut ist.
  10. Lichtempfindliches Silberhalogenidmaterial gemäss Anspruch 1, wobei die Silberhalogenidkörner der Silberhalogenid-Emulsionsschicht Silberchlorid, Silberchlorbromid, Silberiodbromid oder Silberiodchlorbromid sind.
  11. Lichtempfindliches Silberhalogenidmaterial gemäss Anspruch 10, wobei die Silberhalogenidkörner mindestens 60 mol-% Silberchlorid umfassen.
  12. Lichtempfindliches Silberhalogenidmaterial gemäss Anspruch 10, wobei die Silberhalogenidkörner mindestens 70 mol-% Silberbromid mit einem Silberiodidgehalt von nicht mehr als 10 mol-% umfassen.
  13. Lichtempfindliches Silberhalogenidmaterial gemäss Anspruch 10, wobei die Silberhalogenidkörner eine mittlere Korngrösse von 0,7 µm oder weniger aufweisen.
EP93109290A 1993-06-09 1993-06-09 Photographisches Silberhalogenidmaterial Expired - Lifetime EP0628861B1 (de)

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Citations (2)

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Publication number Priority date Publication date Assignee Title
EP0591833A1 (de) * 1992-10-06 1994-04-13 Fuji Photo Film Co., Ltd. Photographisches lichtempfindliches Silberhalogenidmaterial
EP0598315A1 (de) * 1992-11-12 1994-05-25 Fuji Photo Film Co., Ltd. Photographische lichtempfindliche Silberhalogenidmaterialien

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US4937160A (en) * 1988-08-27 1990-06-26 E. I. Du Pont De Nemours And Company Photographic silver halide elements containing aryl hydrazides
JP3041736B2 (ja) * 1991-11-01 2000-05-15 コニカ株式会社 ハロゲン化銀写真感光材料

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0591833A1 (de) * 1992-10-06 1994-04-13 Fuji Photo Film Co., Ltd. Photographisches lichtempfindliches Silberhalogenidmaterial
EP0598315A1 (de) * 1992-11-12 1994-05-25 Fuji Photo Film Co., Ltd. Photographische lichtempfindliche Silberhalogenidmaterialien

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