EP0397167B1 - Verfahren zur Bildherstellung - Google Patents

Verfahren zur Bildherstellung Download PDF

Info

Publication number
EP0397167B1
EP0397167B1 EP90108809A EP90108809A EP0397167B1 EP 0397167 B1 EP0397167 B1 EP 0397167B1 EP 90108809 A EP90108809 A EP 90108809A EP 90108809 A EP90108809 A EP 90108809A EP 0397167 B1 EP0397167 B1 EP 0397167B1
Authority
EP
European Patent Office
Prior art keywords
group
developer
mol
substituted
hydrogen atom
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP90108809A
Other languages
English (en)
French (fr)
Other versions
EP0397167A3 (de
EP0397167A2 (de
Inventor
Yoshihiro Takagi
Mitsunori Hirano
Senzo Sasaoka
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujifilm Holdings Corp
Original Assignee
Fuji Photo Film Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP1116832A external-priority patent/JPH02294637A/ja
Priority claimed from JP1116833A external-priority patent/JP2887367B2/ja
Application filed by Fuji Photo Film Co Ltd filed Critical Fuji Photo Film Co Ltd
Publication of EP0397167A2 publication Critical patent/EP0397167A2/de
Publication of EP0397167A3 publication Critical patent/EP0397167A3/de
Application granted granted Critical
Publication of EP0397167B1 publication Critical patent/EP0397167B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/29—Development processes or agents therefor
    • G03C5/305—Additives other than developers
    • 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
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/10—Organic substances
    • G03C2001/108—Nucleation accelerating compound

Definitions

  • the present invention relates to a method for rapidly forming black-and-white negative images of high contrast in a silver halide photographic material for use in the field of photomechanical processing, using a developer of high stability.
  • the lith developer contains hydroquinone alone as a developing agent, and contains a sulfite which functions as a preservative in the form of the formaldehyde adduct.
  • the free sulfite ion concentration is thereby reduced to about less than 0.1 mol/liter such that the infectious developability characteristic of hydroquinone is not inhibited by sulfite ion. Consequently, the lith developer is extremely prone to air oxidation, such that it cannot be stored for longer than 3 days.
  • an original used in the line drawing photographing step is prepared by combining photocomposed letters, handwritten letters, illustrations and halftone photographs, such that the original contains a mixture of images differing in density and line width.
  • the development of process cameras, photographic light-sensitive materials and image forming methods for use in duplicating line originals with good reproducibility has been strongly desired.
  • enlargement of halftone photographs (“spread") or reduction of halftone photographs (“choke”) is generally carried out. Since lines are sparingly present in the photomechanical process using dots in an enlarging condition, photographs of blurred dots are taken.
  • FR-A-2 402 229 discloses a method for obtaining an image of very high contrast using an imagewise exposed photosensitive material comprising a support having thereon a silver halide emulsion layer comprising processing the photosensitive material with a developer containing sulfite ions and dihydroxy benzene, a hydrazine derivative and at least one polyalkylene oxide having a molecular weight of at least 600.
  • the development may be conducted in the presence of a benzotriazole e.g. 5-methylbenzotriazole.
  • a first object of the present invention is to provide a silver halide photographic material having excellent reproducibility of image lines and dots; namely, a photographic material having a wide latitude of exposure.
  • a second object of the present invention is to provide a method of forming a very high contrast image in a processing system containing a hydrazine compound and using a stable developer to provide a stable image forming system.
  • the control of the nucleation development is carried out by adjusting the pH of the developer to 11.2 or lower.
  • a sufficient increase in contrast is normally not brought about by lowering the pH 11.2 or lower, the lowering of the development pH together with the use of a nucleation accelerator can impart satisfactory contrast to the gradation.
  • the present inventors have discovered that the development carried out at a pH of 11.2 or lower inhibits the infectious development such that image expansion is small as compared with development at a higher pH.
  • the development reaction in the image area is generally attended by the release of hydrogen and halogen ions.
  • the lowering of pH due to diffusion of hydrogen ion into the area adjacent to an image, and the diffusion of halogen ions thereinto cause microscopic development inhibition in the adjacent area. It has been also found out that these phenomena are liable to occur in the nucleation development carried out at a pH of 11.2 or lower.
  • JP-A-53-66732 In the nucleation system utilizing hydrazine compounds as disclosed in JP-A-53-66732 (the term "JP-A" as used herein refers to a "published unexamined Japanese patent application"), the addition of benzotriazoles to a developer is essential for the attainment of an increase in contrast without collateral generation of fog.
  • JP-A-53-66731 describes an increase in contrast attained by the use of a developer free from benzotriazoles and adjusted to pH 11.5 or higher, fog tends to be generated and the exposure latitude of such a system is narrow.
  • the improvement of image quality provided by the present invention results from the achievement of the present inventors in increasing contrast through nucleation at a development pH of 11.2 or lower, such that the addition of benzotriazoles to the processing solution is unnecessary.
  • the absence of benzotriazoles from the developer is advantageous because the Br ⁇ and pH dependencies in the developer become great and microscopic development inhibition becomes liable to occur.
  • preferred aliphatic groups represented by R1 include those containing from 1 to 30 carbon atoms, especially straight chain, branched and cyclic alkyl groups containing from 1 to 20 carbon atoms.
  • the branched alkyl groups may be cyclized so as to form a saturated hetero ring containing one or more hetero atoms (nitrogen, sulfur, oxygen).
  • these alkyl groups may be substituted by an aryl group, an alkoxy group, a sulfoxy group, a sulfonamido group or a carbonamide group.
  • the aromatic group represented by R1 contains from 6 to 36 carbon atoms and includes monocyclic and bicyclic aryl groups, and unsaturated heterocyclic groups.
  • the unsaturated heterocyclic group herein may include a hetero aryl group formed by condensation with a monocyclic or bicyclic aryl group.
  • aromatic groups include a benzene ring, a naphtalene ring, a pyridine ring, a pyrimidine ring, an imidazole ring, a pyrazole ring, a quinoline ring, an isoquinoline ring, a benzimidazole ring, a thiazole ring, and a benzothiazole ring.
  • those containing a benzene ring are preferred.
  • Groups particularly preferred as R1 are aryl groups.
  • the aryl group and unsaturated heterocyclic group represented by R1 may be substituted.
  • substituent group include an alkyl group, an aralkyl group, an alkenyl group, an alkynyl 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, a hydroxyl group, a halogen atom, a cyano group, a sulfo group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an acyl group, an alkoxycarbonyl group, an acyloxy group
  • straight chain, branched or cyclic alkyl groups (especially those containing from 1 to 20 carbon atoms), an aralkyl group (especially a monocyclic or dicyclic group having an alkyl moiety containing from 1 to 3 carbon atoms), an alkoxy group (especially those containing from 1 to 20 carbon atoms), a substituted amino group (especially those substituted by an alkyl group containing from 1 to 20 carbon atoms), an acylamino group (especially those containing from 2 to 30 carbon atoms), a sulfonamido group (especially those containing from 1 to 30 carbon atoms), a ureido group (especially those containing from 1 to 30 carbon atoms), and a phosphoric acid amido group (especially those containing from 1 to 30 carbon atoms) are particularly preferred as the substituent.
  • alkyl group represented by R2 in formula (I) those containing from 1 to 4 carbon atoms are preferred.
  • the alkyl group may be substituted by a halogen atom, a cyano group, a carboxy group, a sulfo group, an alkoxy group, a phenyl group, or a sulfonyl group.
  • aryl group represented by R2 monocyclic or bicyclic aryl groups, e.g., those containing from 6 to 36 carbon atoms and a benzene ring, are preferred. Such groups may be substituted by a halogen atom, an alkyl group, a cyano group, a carboxyl group, a sulfo group or a sulfonyl group.
  • alkoxy group represented by R2 those containing from 1 to 8 carbon atoms are preferred, and the alkoxy group may be substituted by a halogen atom or an aryl group.
  • aryloxy group represented by R2 monocyclic groups containing from 6 to 10 carbon atoms are preferred, and these groups may be substituted by, e.g., a halogen atom.
  • substituted groups represented by R2 may be further substituted by an alkyl group, a halogen atom, a cyano group, a nitro group or a carboxyl group.
  • carbamoyl group represented by R2 unsubstituted groups and an alkylcarbamoyl group having from 1 to 10 carbon atoms or an arylcarbamoyl group are preferred.
  • the substituted carbamoyl group may be further substituted by an alkyl group, a halogen atom, a cyano group or a carboxyl group.
  • an alkoxycarbonyl group having from 1 to 10 carbon atoms or an aryloxycarbonyl group are preferred.
  • the oxycarbonyl group may be further substituted by an alkyl group, a halogen atom, a cyano group or a nitro group.
  • G1 represents a carbonyl group
  • a hydrogen atom is most preferred.
  • G1 represents a sulfonyl group
  • R2 include an alkyl group (e.g., methyl), an aralkyl group (e.g., o-hydroxyphenylmethyl), an aryl group (e.g., phenyl) or a substituted amino group (e.g., dimethylamino).
  • G1 represents a sulfoxy group
  • those preferred as R2 include a cyanobenzyl group, and a methylthiobenzyl group.
  • G1 represents those preferred as R2 include a methoxy group, an ethoxy group, a phenoxy group and a phenyl group. In particular, a phenoxy group is preferred.
  • G1 represents an N-substituted or unsubstituted iminomethylene group
  • those preferred as R2 include a methyl group, an ethyl group and a substituted or unsubstituted phenyl group.
  • the substituent groups for R2 include those set forth for R1.
  • R2 may constitute a group which releases the moiety G1-R2 from the residual molecule and undergoes a cyclization reaction resulting in the formation of a cyclic structure containing the moiety -G1-R2, R2 in this case being represented by formula (a): -R3-Z1 (a) wherein Z1 is a group which participates in an intramolecular nucleophilic attack against the group G1 to thereby release the leaving group G1-R3-Z1 from the residual molecule; and R3 is the remaining portion of R2 obtained by eliminating Z1 from R2, and R3 participates in the formation of a cyclic structure together with G1, R3 and Z1 upon the intramolecular nucleophilic attack of Z1 upon G1.
  • Z1 examples include functional groups capable of reacting directly with the group G1, such as -OH, -SH, -NHR4 (wherein R4 represents a hydrogen atom, an alkyl group, an aryl group, -COR5 or -SO2R5; and R5 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group), or -COOH (wherein -OH, -SH, -NHR4 and -COOH may be temporarily protected so as to produce these groups by hydrolysis using an alkali or the like), and functional groups which react with the group G1 by reaction with a nucleophilic reagent (e.g., hydroxide ion, sulfite ion), such as (wherein R6 and R7 each represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group).
  • a nucleophilic reagent e.g., hydroxide
  • a ring formed by the group G1, R3 and Z1 is preferably a 5- or 6-membered ring.
  • R b 1 to R b 4 may be the same or different, each being a hydrogen atom, an alkyl group (preferably containing 1 to 12 carbon atoms), an alkenyl group (preferably containing 2 to 12 carbon atoms), an aryl group (preferably containing 6 to 12 carbon atoms);
  • B represents an atomic group necessary to complete a 5- or 6-membered ring which may be substituted;
  • m and n each represents 0 or 1, provided that n+m is 1 or 2.
  • Specific examples of the 5- or 6-membered ring completed by B include a cyclohexene ring, a cycloheptene ring, a benzene ring, a naphthalene ring, a pyridine ring, and a quinoline ring.
  • Z1 has the same meaning as in formula (a). wherein R c 1 and R c 2 may be the same or different, each being a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a halogen atom.
  • R c 3 represents a hydrogen atom, an alkyl group, an alkenyl group or an aryl group.
  • p represents 0 or 1
  • q represents an integer of from 1 to 4.
  • R c 1 , R c 2 and R c 3 may combine to form a ring with the proviso that the resulting structure allows for the intramolecular nucleophilic attack of Z1 on the group G1.
  • R c 1 and R c 2 each is preferably a hydrogen atom, a halogen atom or an alkyl group, and R c 3 is preferably an alkyl group or an aryl group.
  • q is preferably an integer of from 1 to 3.
  • CR c 1 R c 2 may be the same or different.
  • Z1 has the same meaning as in formula (a).
  • both of A1 and A2 represent a hydrogen atom, or either one of A1 and A2 is a hydrogen atom and the other represents a substituted or unsubstituted alkylsulfonyl group containing up to 20 carbon atoms, a substituted or unsubstituted arylsulfonyl group (preferably including a phenylsulfonyl group and a phenylsulfonyl group substituted to provide a sum of Hammett's sigma values of -0.5 or above), or a substituted or unsubstituted acyl group containing preferably up to 20 carbon atoms (preferably including a benzoyl group, a benzoyl group substituted to provide a sum of Hammett's sigma values of -0.5 or above, and an acyl group substituted by a straight chain, branched or cyclic, unsubstituted or substituted aliphatic acyl group (wherein
  • each of A1 and A2 is a hydrogen atom.
  • ballast group containing a nondiffusible photographic additive such as a coupler may be introduced into the groups R1 or R2 of formula (I).
  • the ballast group is a group containing at least 8 carbon atoms which does not substantially effect the photographic properties, and can be chosen from among an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group, an alkylphenoxy group, etc.
  • a moiety which promotes the adsorption of the compound of formula (I) to the surface of silver halide grain may be introduced into the groups R1 or R2 of formula (I).
  • adsorption groups include thiourea groups, heterocyclic thioamido groups, heterocyclic mercapto groups, triazole groups, etc., as disclosed in US-A- 4,385,108 and 4,459,347, JP-A-59-195233, JP-A-59-200231, JP-A-59-201045, JP-A-59-201046, JP-A-59-201047, JP-A-59-201048, JP-A-59-201049, JP-A-61-170733, JP-A-61-270744, JP-A-62-948, JP-A-63-234244, JP-A-63-234245 and JP-A-63-234246.
  • 63-147339, 63-179760, 63-229163, 1-18377, 1-18378, 1-18379, 1-15755, 1-16814, 1-40792, 1-42615 and 1-42616 can be employed as the hydrazine derivative for use in the present invention.
  • the hydrazine derivative used in the present invention is added to a unit area of the photosensitive material in an amount of from 1 ⁇ 10 ⁇ 6 mol to 5 ⁇ 10 ⁇ mol, and particularly preferably from 1 ⁇ 10 ⁇ 5 to 2 ⁇ 10 ⁇ mol, per mol of silver halide.
  • Incorporation of the hydrazine derivative of formula (I) into a photographic light-sensitive material may be accomplished by first dissolving a water-soluble hydrazine derivative into water, or by dissolving other hydrazine derivatives insoluble in water into a water-miscible organic solvent, such as an alcohol (e.g., methanol, ethanol), ester (e.g., ethyl acetate), ketone (e.g., acetone), etc., and then adding the resulting solution to a silver halide emulsion or hydrophilic colloid solution.
  • a water-soluble hydrazine derivative into water
  • a water-miscible organic solvent such as an alcohol (e.g., methanol, ethanol), ester (e.g., ethyl acetate), ketone (e.g., acetone), etc.
  • the hydrazine derivative can be added to the emulsion at any stage of preparation from the beginning of chemical ripening to coating, but is preferably added after the conclusion of chemical ripening, and more preferably the hydrazine derivative is added to the coating composition ready for coating.
  • the hydrazine derivative is contained in a silver halide emulsion layer.
  • the silver halide photographic material preferably contains at least one dye having an absorption maximum in the wavelength region of from 300 to 420 nm.
  • dyes having an absorption peak in the wavelength region from 300 nm to 420 nm those having an absorption peak in the wavelength region from 350 nm to 410 nm (including ultraviolet absorbing agents) are preferred.
  • Useful examples thereof include the dyes disclosed in JP-A-62-210458, JP-A-63-104046, JP-A-63-103235, JP-A-63-208846, JP-A-1-61745, JP-A-63-306436 and JP-A-63-314535.
  • benzotriazole compounds substituted by aryl groups, 4-thiazolidone compounds, benzophenone compounds, cinnamic ester compounds, butadiene compounds, benzoxazole compounds, ultraviolet absorbing polymers can be employed as the dye having an absorption peak in the wavelength region from 300 to 420 nm.
  • Dyes which are particularly preferably employed in the present invention include the compounds represented by the following formulae (D-a), (D-b), (D-c) and (D-d), having an absorption maximum in the wavelength region from 300 nm to 420 nm.
  • R1 ⁇ is a group represented by -OX or and X and Y each represents a hydrogen atom, an alkyl group, or a substituted alkyl group such as a cyanoalkyl group, a carboxyalkyl group, a sulfoalkyl group, a hydroxyalkyl group, a halogenated alkyl group, or a sodium or potassium salt thereof.
  • R2 ⁇ and R3 ⁇ each represents a hydrogen atom, a halogen atom, an alkyl group, a hydroxy group, an alkoxy group, an alkylthio group, or has the same meaning as the foregoing group -OX.
  • Q represents a phenyl group substituted by at least one halogen atom, carboxyl group, sulfo group, sulfoalkyl group, or sodium or potassium salt thereof, a sulfoalkyl group, a sulfoalkoxyalkyl group, or a sulfoalkylthioalkyl group.
  • L represents a methine group which may be substituted.
  • R4 ⁇ represents an alkyl group, a carboxyl group, an alkyloxycarbonyl group, or an acyl-substituted or unsubstituted amino group.
  • m represents 1 or 2
  • n represents 0 or 1.
  • R5 ⁇ , R6 ⁇ , R8 ⁇ , R9 ⁇ and R10 ⁇ each represents a hydrogen atom, a halogen atom, an alkyl group, a hydroxyl group, an alkoxy group, an amino group, an acylamino group, or a carboxyl or sulfo group or its sodium or potassium salt.
  • R7 ⁇ represents an alkyl group or a carboxyl group.
  • R11 ⁇ and R12 ⁇ each represents an unsubstituted or substituted alkyl group, an aryl group, an alkoxycarbonyl group, or a carboxyl group
  • R13 ⁇ and R14 ⁇ each represents an alkyl group substituted by a sulfo group or a carboxyl group, an aryl group substituted by a sulfo group or a carboxyl group, or a sodium or potassium salt thereof.
  • L represents a substituted or unsubstituted methine chain
  • M represents a sodium, potassium or hydrogen atom.
  • l represents 0 or 1.
  • R1′′′, R2′′′, R3′′′,and R4′′′ each represents an alkyl group, a hydroxyalkyl group, a cyano group, an alkylcyano group, an alkoxy group, or a sulfoalkyl group.
  • R5′′′ and R6′′′ each represents a sulfo group or an alkylsulfo group.
  • the above-described dyes having an absorption maximum in the wavelength region of from 300 to 420 nm may be contained in any constituent layer including an emulsion layer, an interlayer, a protective layer or other hydrophilic colloid layer of the photosensitive material.
  • the dye may be substantially fixed to a desired layer by means of, e.g., a mordant.
  • the dye is contained in a protective layer.
  • mordants used for fixing these dyes include those disclosed in JP-B-43-10254 (the term "JP-B” as used herein refers to an "examined Japanese patent publication"), US-A- 2,548,564, 2,882,156 and 3,444,138.
  • dispersion of microcrystalline solid grains of a dye as disclosed in WO-8804794 can be used in the present invention.
  • useful dyes include the functional dyes disclosed in JP-A-63-208846, JP-A-1-61745, said dyes undergoing decolorization in a developer.
  • the addition amount of the dye having an absorption maximum in the wavelength region of from 300 to 420 nm depends on the molar absorptivity, but generally ranges from 10 ⁇ g/m to 1 g/m, and preferably from 50 mg/m to 500 mg/m of the photosensitive material.
  • the above-described dyes can be dissolved in proper solvents (e.g., water, alcohols such as methanol, ethanol, propanol, etc., acetone, methyl cellosolve, mixtures of two or more thereof), and then added to a coating composition for a hydrophilic colloid layer of the present invention.
  • proper solvents e.g., water, alcohols such as methanol, ethanol, propanol, etc., acetone, methyl cellosolve, mixtures of two or more thereof.
  • the above-described dyes i.e., ultraviolet absorbents
  • Determination of the gamma value may be made using any B/W (black-and-white) developer as long as the pH of the developer is adjusted to 11.2 or lower. In the evaluation, a development temperature of 38°C and a development time of 30 seconds are adopted.
  • the term "gamma value" as used herein is defined as a ratio of the difference in density to a difference between an exposure required for providing a density of 3.0 and an exposure required for providing a density of 0.1 ( ⁇ log E).
  • At least one nucleation accelerator selected from the compounds represented by formula (II) and formula (III) is preferably incorporated into the light-sensitive material.
  • Y-[(X) n -A-B] m (II) wherein Y represents a group which adsorbs to a silver halide; X represents a hydrogen atom or a divalent linking group; A represents a divalent linkage group; B represents an amino group (which may be substituted), an ammonium group, or a nitrogen-containing heterocyclic group; m represents 1, 2 or 3; and n represents 0 or 1.
  • Examples of the group represented by Y which adsorbs to a silver halide include nitrogen-containing heterocyclic compound residues.
  • formula (II) is represented by the following formula (II-a): wherein l represents 0 or 1, m represents 1, 2 or 3, and n represents 0 or 1.
  • [(X) n -A-B] m has the same meaning as in formula (II), and Q represents an atomic group including at least one kind of constituent atom selected from carbon, nitrogen, oxygen and sulfur atoms to complete a 5- or 6-membered hetero ring, which may be fused together with an aromatic carbon ring or an aromatic hetero ring.
  • the heterocyclic ring completed by Q includes a substituted or unsubstituted indazole, benzimidazole, benzotriazole, benzoxazole, benzothiazole, imidazole, thiazole, oxazole, triazole, tetrazole, azaindene, pyrazole, indole, triazine, pyrimidine, pyridine, or quinoline.
  • M represents a hydrogen atom, an alkali metal atom (e.g., sodium, potassium), an ammonium group (e.g., trimethylammonium, dimethylbenzylammonium), or a group capable of being converted to a hydrogen or alkali metal atom under alkaline condition (e.g., acetyl, cyanoethyl, methanesulfonylethyl).
  • an alkali metal atom e.g., sodium, potassium
  • an ammonium group e.g., trimethylammonium, dimethylbenzylammonium
  • a group capable of being converted to a hydrogen or alkali metal atom under alkaline condition e.g., acetyl, cyanoethyl, methanesulfonylethyl.
  • heterocyclic rings may be substituted by a nitro group, a halogen atom (e.g., chlorine, bromine), a mercapto group, a cyano group, a substituted or unsubstituted alkyl group (e.g., methyl, ethyl, propyl, t-butyl, cyanoethyl, methoxyethyl, methylthioethyl), a substituted or unsubstituted aryl group (e.g., phenyl, 4-methanesulfonamidophenyl, 4-methylphenyl, 3,4-dichlorophenyl, naphthyl), a substituted or unsubstituted alkenyl group (e.g., allyl), a substituted or unsubstituted aralkyl group (e.g., benzyl, 4-methylbenzyl, phenethyl), a substituted or unsubstit
  • Examples of the divalent linkage group represented by X include -S-, -O-,
  • the divalent linkage group represented by X may be attached to Q via a straight chain or branched alkylene group (e.g., methylene, ethylene, propylene, butylene, hexylene, 1-methylethylene).
  • R1, R2, R3, R4, R5, R6, R7, R8, R9 and R10 each represents a hydrogen atom, a substituted or unsubstituted alkyl group (e.g., methyl, ethyl, propyl, n-butyl), a substituted or unsubstituted aryl group (e.g., phenyl, 2-methylphenyl), a substituted or unsubstituted alkenyl group (e.g., propenyl, 1-methylvinyl), or a substituted or unsubstituted aralkyl group (e.g., benzyl, phenethyl).
  • a substituted or unsubstituted alkyl group e.g., methyl, ethyl, propyl, n-butyl
  • a substituted or unsubstituted aryl group e.g., phenyl, 2-methylphenyl
  • A represents a divalent linkage group, specific examples of which include a straight chain or branched alkylene group having from 1 to 10, preferably from 1 to 6, most preferably from 2 to 4 carbon atoms (e.g., methylene, ethylene, propylene, butylene, hexylene, 1-methylethylene), a straight chain or branched alkenylene group having from 2 to 10, preferably from 2 to 6 carbon atoms (e.g., vinylene, 1-methylvinylene), a straight chain or branched aralkylene group having from 7 to 18, preferably from 7 to 11 carbon atoms (e.g., benzylidene) and an arylene group having from 6 to 18, preferably from 6 to 10 carbon atoms (e.g., phenylene, naphthylene).
  • Each of the above groups represented by A may be further substituted.
  • the amino group (which may be substituted) represented by B includes those having formula (II-b): wherein R11 and R1 may be the same or different, and each represents a hydrogen atom, a substituted or unsubstituted alkyl, alkenyl or aralkyl group having from 1 to 30 carbon atoms.
  • These groups may assume a straight chain form (e.g., methyl, ethyl, n-propyl, n-butyl, n-octyl, allyl, 3-butenyl, benzyl, 1-naphthylmethyl), a branched form (e.g., isopropyl, t-octyl), or a cyclic form (e.g., cyclohexyl).
  • a straight chain form e.g., methyl, ethyl, n-propyl, n-butyl, n-octyl, allyl, 3-butenyl, benzyl, 1-naphthylmethyl
  • a branched form e.g., isopropyl, t-octyl
  • a cyclic form e.g., cyclohexyl
  • R11 and R1 may combine together to form a ring.
  • the ring may be a saturated hetero ring containing one or more hetero atoms (including oxygen, sulfur or nitrogen), specific examples thereof including a pyrrolidyl group, a piperidyl group and a morpholino group.
  • substituent groups for the groups represented by R11 and R1 include a carboxyl group, a sulfo group, a cyano group, a halogen atom (e.g., fluorine, chlorine, bromine), a hydroxyl group, an alkoxycarbonyl group containing not more than 20 carbon atoms (e.g., methoxycarbonyl, ethoxycarbonyl, phenoxycarbonyl, benzyloxycarbonyl), an alkoxy group containing not more than 20 carbon atoms (e.g., methoxy, ethoxy, benzyloxy, phenethyloxy), a monocyclic aryloxy group containing not more than 20 carbon atoms (e.g., phenoxy, p-tolyloxy), an acyloxy group containing not more than 20 carbon atoms (e.g., acetyloxy, propionyloxy), an acyl group containing not more than 20 carbon atoms
  • the ammonium group represented by B includes those of formula (II-c): wherein R13, R14 and R15 each has the same meaning as R11 or R1 in formula (II-b); and Z ⁇ represents an anion, such as a halide ion (e.g., Cl ⁇ , Br ⁇ , I ⁇ ), a sulfonate ion (e.g., trifluoromethanesulfonate, p-toluenesulfonate, benzenesulfonate, p-chlorobenzenesulfonate), a sulfate ion (e.g., ethylsulfate, methylsulfate), perchlorate or tetrafluoroborate; and p represents 0 or 1, but p is 0 when the compound forms an inner salt.
  • a halide ion e.g., Cl ⁇ , Br ⁇ , I ⁇
  • the nitrogen-containing heterocyclic group represented by B is a 5- or 6-membered ring residue containing at least one nitrogen atom.
  • the ring residue may be substituted, or the ring residue may be fused together with another ring.
  • Examples of such a heterocyclic group include an imidazolyl group, a pyridyl group and a thiazolyl group.
  • heterocyclic rings may each be substituted by a substituent group as described for the hetero ring of formula (II).
  • R1 and R each represents a hydrogen atom, or an aliphatic group, or R1 and R combine together to form a ring
  • R3 represents a divalent aliphatic group
  • X represents a divalent nitrogen-, oxygen- or sulfur-containing heterocyclic group
  • n represents 0 or 1
  • M represents a hydrogen atom, an alkali metal, an alkaline earth metal, a quaternary ammonium salt, a quaternary phosphonium salt, or an amidino group.
  • Aliphatic groups preferably represented by R1 and R include alkyl, alkenyl and alkynyl groups having from 1 to 12 carbon atoms (each of which may be substituted).
  • alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a decyl group, a dodecyl group, an isopropyl group, a sec-butyl group, a cyclohexyl group, etc.
  • Examples of the alkenyl group include an allyl group, a 2-butenyl group, a 2-hexenyl group, a 2-octenyl group, etc.
  • alkynyl group examples include a propargyl group, a 2-pentinyl group, etc.
  • Substituent for the above-cited groups include a phenyl group, a substituted phenyl group, an alkoxyl group, an alkylthio group, a hydroxy group, a carboxyl group, a sulfo group, an alkylamino group and an amido group.
  • the ring thus formed is preferably a 5- or 6-membered hetero ring formed of combinations of carbon, nitrogen, and/or oxygen atoms, and is particularly preferably a saturated ring, e.g., etc.
  • Groups which are particularly preferred as R1 and R include an alkyl group having from 1 to 3 carbon atoms, especially an ethyl group.
  • the divalent aliphatic group represented by R3 is preferably -R4- or -R4S-.
  • the number of carbon atoms in the group R4 is preferably from 2 to 4, and groups which are particularly preferred as R4 include -CH2CH2- and -CH2CH2CH2-. When n of (X) n is 0, however, R3 represents -R4- alone.
  • Examples of the divalent heterocyclic group represented by X include 5- and 6-membered hetero rings containing a nitrogen, oxygen or sulfur atom, which rings may be fused together with a benzene ring.
  • Specific examples of such hetero rings include tetrazole, triazole, thiadiazole, oxadiazole, imidazole, thiazole, oxazole, benzimidazole, benzothiazole, benzoxazole, etc.
  • tetrazole and thiadiazole are preferred.
  • the alkali metal represented by M includes Na+, K+, Li+, etc.
  • the alkaline earth metal represented by M includes Ca++, Mg++, etc.
  • the quaternary ammonium salt represented by M includes those containing from 4 to 30 carbon atoms, such as (CH3)4N+, (C2H5)4N+, (C4H9)4N+, C6H5CH2N+(CH3)3 and C16H33N+(CH3)3.
  • the quaternary phosphonium salt represented by M contains from 4 to 20 carbon atoms and includes (C4H9)4P+, C16H33P+(CH3)3, C6H5CH2P+(CH3)3.
  • Examples of the inorganic acid salt of the compound represented by formula (III) include hydrochloride, sulfate and phosphate, and examples of the organic acid salt thereof include acetate, propionate, methanesulfonate, benzenesulfonate and p-toluenesulfonate.
  • III-8 (HOCH2CH2)2NCH2CH2SH
  • nucleation accelerator represented by formulae (II) and (III) depends on the particular compound selected, but is generally in the range of from 1.0 ⁇ 10 ⁇ 3 to 0.5 g/m, and preferably from 5.0 ⁇ 10 ⁇ 3 to 0.3 g/m.
  • the nucleation accelerator is dissolved in a proper solvent (e.g., water, alcohols such as methanol and ethanol, acetone, dimethylformamide, methyl cellosolve), and then added to a coating composition of a hydrophilic colloid layer of the photosensitive material.
  • a proper solvent e.g., water, alcohols such as methanol and ethanol, acetone, dimethylformamide, methyl cellosolve
  • the nucleation accelerator is contained in a silver halide emulsion layer.
  • Two or more nucleation accelerators may be used in combination.
  • the silver halide emulsion for use in the present invention may be prepared using a known method such as a neutral method, an acid method, an ammonia method, a simple single jet method, a reverse single jet method, a double jet method, a controlled double jet method, a core/shell method, etc., described, e.g., in T.H. James, The Theory of the Photographic Process , 4th Ed., pp. 88 to 104, Macmillan (1977).
  • the grain size, grain shape and the distribution of the grain size can be controlled by the use of a silver halide solvent, such as a thioether and thiourea, if desired.
  • a silver halide solvent such as a thioether and thiourea
  • the silver halide grains of the present invention are not particularly limited with respect to grain size, grain size distribution, crystal habit, crystal form (regular, twin). However, the silver halide grains are preferably relatively uniform in grain size, and the preferred grain size ranges from 0.05 to 0.8 ⁇ m.
  • a monodisperse grain size distribution is preferred in the present invention.
  • the terminology "monodisperse system” as used herein refers to a system wherein 95% of the grains are within the range of ⁇ 60% of the number average grain size, and preferably within ⁇ 40%.
  • the silver halide grains are not particularly limited with respect to crystal habit, crystal form and the like, but preferably have a cubic form, an octahedral form, a tetradecahedral form or a mixture of two or more thereof, and particularly preferably constitute a cubic form.
  • the halogen composition of the silver halide grains silver bromide, silver iodobromide, silver chlorobromide and silver chloroiodobromide are preferred.
  • the bromide content is preferably at least 70 mol%, and particularly preferably at least 90 mol%.
  • the iodide content is generally up to 10 mol%, and preferably up to 5 mol%.
  • cadmium salts zinc salts, lead salts, thallium salts, rhodium salts or complexes thereof, iridium salts or complexes thereof may be present.
  • an iridium salt and a rhodium salt is each preferably added in an amount of from 10 ⁇ 8 to 10 ⁇ 5 mol/mol Ag and from 10 ⁇ 8 to 10 ⁇ 4 mol/mol Ag, respectively.
  • the silver halide emulsion of the present invention may be chemically sensitized, or may be used in a chemically unsensitized condition.
  • the silver halide emulsion used in the present invention may be chemically sensitized using sulfur sensitization by, e.g., sodium thiosulfate, thioureas, etc.; noble metal sensitization by, e.g., chloroaurates, gold trichloride and the like as gold sensitizers, palladium chloride and chloropalladates as palladium sensitizers, platinum compounds, iridium compounds, etc.; selenium sensitization by, e.g., selenious acid, selenourea, etc.; and reduction sensitization by, e.g., stannous chloride, polyamines such as diethylenetriamine, sulfites and silver nitrate.
  • the above described chemical sensitizers can be used alone or in combination thereof.
  • Sensitizing dyes for use in the present invention include various dyes well known in the field of photographic materials, such as cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes.
  • cyanine dyes cyanine dyes, merocyanine dyes and complex merocyanine dyes. Any nuclei generally present in the cyanine dyes can constitute the basic heterocyclic nuclei of these dyes.
  • useful basic heterocyclic nuclei include pyrroline, oxazoline, thiazoline, pyrrole, oxazole, thiazole, selenazole, imidazole, tetrazole and pyridine; nuclei formed by fusing together one of the above-described nuclei and an alicyclic hydrocarbon ring; and nuclei formed by fusing together one of the above-described nuclei and an aromatic hydrocarbon ring.
  • nuclei examples include indolenine, benzindolenine, indole, benzoxazole, naphthoxazole, benzothiazole, naphthothiazole, benzoselenazole, benzimidazole and quinoline.
  • the carbon atoms of these nuclei may be substituted.
  • the merocyanine dyes or the complex merocyanine dyes can contain 5- or 6-membered heterocyclic nuclei, such as pyrazoline-5-one, thiohydantoin, 2-thio-oxazolidine-2,4-dione, thiazolidine-2,4-dione, rhodanine and thiobarbituric acid, as ketomethylene structure-containing nuclei.
  • useful sensitizing dyes are disclosed, e.g., in DE-C- 929,080, US-A-2,231,658, 2,493,748, 2,503,776, 2,519,001, 2,912,329, 3,656,959, 3,672,897 and 3,694,217, GB-B-1,242,588, JP-B-44-14030, JP-A-53-137133, JP-A-55-45015, and JP-A-62-235947.
  • sensitizing dyes may be employed individually or in combination. Combinations of sensitizing dyes are often employed for the purpose of supersensitization.
  • Substances which exhibit a supersensitizing effect in combination with another sensitizing dye although they themselves do not spectrally sensitize silver halide emulsions or do not absorb light in the visible region may be incorporated into the silver halide emulsions of the present invention.
  • the sensitizing dyes and the like are applicable to a photographic emulsion through the addition thereto at any stage of the emulsion preparation. Also, the sensitizing dyes may be added to the emulsion at any stage between at the conclusion of emulsion preparation and just before the emulsion coating.
  • the emulsion preparation comprises grain formation, physical ripening and chemical ripening stages.
  • Sensitizing dyes for use in the present invention are added to the silver halide emulsion in the form of aqueous solution, or as a solution in a water-miscible organic solvent, such as methanol, ethanol, propyl alcohol, methyl cellosolve and pyridine.
  • a water-miscible organic solvent such as methanol, ethanol, propyl alcohol, methyl cellosolve and pyridine.
  • the sensitizing dye is generally added to emulsion before the coating of the emulsion on a support. However, the sensitizing dye may be added during the chemical ripening or grain formation stage.
  • the sensitizing dyes are added to the silver halide emulsion of the present invention in an amount of from 10-6 to 10 ⁇ 1 mol, and preferably from 10 ⁇ 4 to 10 ⁇ mol, per mol of silver.
  • the photographic material used in the present invention can contain a variety of compounds for the purpose of preventing fog or stabilizing photographic properties during production, storage, or photographic processing.
  • azoles such as benzothiazolium salts, nitroindazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, aminotriazoles, benzothiazoles, nitrobenzotriazoles; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolidinethiones; azaindenes such as triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a,7)tetraazaindenes), pentaazaindenes; and compounds which are known as antifoggant or stabilizers, such as benzene-thiosulfonic acid, benzenes
  • nitroindazoles e.g., 5-nitroindazole
  • hydroquinone derivatives e.g., hydroquinone, methylhydroquinone
  • these compounds may also be contained in a processing solution.
  • the effect of benzotriazoles on image quality differs depending on whether the benzotriazole is present in a photographic material or in a processing solution. While the presence of benzotriazole in a processing solution results in the deterioration of image quality, the use of a benzotriazole in the photographic material exerts little influence upon image quality, but rather produces a fog inhibiting effect.
  • the photographic light-sensitive material used in the present invention may contain an inorganic or organic hardener in the photographic emulsion layers or other hydrophilic colloid layers.
  • specific examples of such hardeners include active vinyl compounds (e.g., 1,3,5-triacryloylhexahydro-s-triazine, 1,3-vinylsulfonyl-2-propanol), active halogen compounds (e.g., 2,4-dichloro-6-hydroxy-s-triazine) and mucohalogenic acids. These hardeners can be used alone, or as mixture of two or more thereof.
  • active vinyl compounds disclosed in JP-A-53-42112, JP-A-53-57257, JP-A-59-162546 and JP-A-60-80846, and active halogen compounds disclosed in US-A- 3,325,287 are preferred.
  • the photographic emulsion layers and other hydrophilic colloid layers of the photographic material used in the present invention may contain various surface active agents used for a variety of purposes, including, for example, as a coating aid, prevention of electrification, improvement in slip property, emulsifying dispersion, prevention of adhesion, improvements in photographic characteristics (e.g., acceleration of development, increase in contrast, sensitization).
  • various surface active agents used for a variety of purposes, including, for example, as a coating aid, prevention of electrification, improvement in slip property, emulsifying dispersion, prevention of adhesion, improvements in photographic characteristics (e.g., acceleration of development, increase in contrast, sensitization).
  • Preferred surface active agents for use in the present invention are polyalkylene oxides having a molecular weight of 600 or more disclosed in JP-B-58-9412.
  • the fluorine-containing compounds disclosed in US-A- 4,201,586 and JP-A-60-80849, for example, are especially preferred.
  • the photographic emulsion used in the present invention may contain a dispersion of a synthetic polymer insoluble or slightly soluble in water.
  • Synthetic polymers useful for the above-described purpose include those containing constituent repeating units derived from an alkyl (meth)acrylate, an alkoxyalkyl (meth)acrylate, glycidyl (meth)acrylate, alone or in combination thereof, or in combination with repeating units derived from acrylic acid and methacrylic acid.
  • the photographic light-sensitive material used in the present invention may contain, in a photographic emulsion layer or other hydrophilic colloid layer, a hydroquinone derivative (e.g., a DIR hydroquinone) which releases a development inhibitor in proportion to the image density upon development.
  • a hydroquinone derivative e.g., a DIR hydroquinone
  • the silver halide emulsion and other layers of the photographic light-sensitive material used in the present invention preferably contain a compound having an acid group.
  • useful acid group-containing compounds include, for example, organic acids, such as salicylic acid, acetic acid, and ascorbic acid, and homopolymers and copolymers having constituent repeating units derived from an acid monomer such as acrylic acid, maleic acid and phthalic acid.
  • organic acids such as salicylic acid, acetic acid, and ascorbic acid
  • homopolymers and copolymers having constituent repeating units derived from an acid monomer such as acrylic acid, maleic acid and phthalic acid for details regarding these compounds, the descriptions in JP-A-61-228437, JP-A-62-25745 and JP-A-62-55642 can be referred to.
  • ascorbic acid is particularly preferred, while among the high molecular weight acid group-containing compounds, water-dispersible latexes of copolymers prepared from acid monomers such as acrylic acid, and crosslinking monomers having two or more unsaturated groups such as divinylbenzene provide a particularly desirable effect.
  • gelatin is used to great advantage.
  • other hydrophilic colloids can also be used.
  • gelatin lime-processed gelatin, acid-processed gelatin, and gelatin derivatives can be used. Details of useful gelatins are described in Research Disclosure , Vol. 176, No. 17643, Item IX (December, 1978).
  • the light-sensitive material used in the present invention can include hydrophilic colloid layers such as a surface protecting layer, an interlayer, a filter layer and an antihalation layer, in addition to a silver halide emulsion layer.
  • the light-sensitive material used in the present invention can include a backing layer for the purpose of distinguishing the light-sensitive surface side from the back side, and for preventing curling and halation, etc.
  • the backing layer preferably contains a matting agent having a relatively large average particle size in order to provide adhesion resistance.
  • a preferred average particle size ranges from 1.0 to 10 ⁇ m, particularly from 2.0 to 5.0 ⁇ m.
  • the surface protecting layer used in the present invention can contain a matting agent such as methyl methacrylate homopolymer, methyl methacrylate-methacrylic acid copolymer and, magnesium oxide, and a slipping agents such as a silicone compound disclosed in US-A- 3,489,576 and 4,047,958, colloidal silica disclosed in JP-B-56-23139, paraffin wax, higher fatty acid esters, and starch,
  • a matting agent such as methyl methacrylate homopolymer, methyl methacrylate-methacrylic acid copolymer and, magnesium oxide
  • a slipping agents such as a silicone compound disclosed in US-A- 3,489,576 and 4,047,958, colloidal silica disclosed in JP-B-56-23139, paraffin wax, higher fatty acid esters, and starch
  • hydrophilic colloid layers can contain, as a plasticizer, polyols such as trimethylolpropane, pentanediol, butanediol, ethylene glycol, glycerine and the like.
  • the silver halide light-sensitive material used in the present invention provides a high contrast black-and-white image using a developer which contains at least 0.20 mol/liter of sulfite ion as a preservative, and has a pH of 11.2 or lower, and more preferably a pH of from 11.0 to 9.5
  • the developer for use in the present invention is not particularly limited with respect to developing agent.
  • the developing agent preferably is selected from the dihydroxybenzenes.
  • the combined use of dihydroxybenzenes and 1-phenyl-3-pyrazolidones, or the combined use of dihydroxybenzenes and p-aminophenols is preferable.
  • Developing agents of the dihydroxybenzene type for use in the present invention include hydroquinone, chlorohydroquinone, isopropylhydroquinone, methylhydroquinone, etc.
  • hydroquinone is preferred.
  • Developing agents of the 1-phenyl-3-pyrazolidone type or a derivative thereof for use in the present invention include 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, and 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone.
  • Developing agents of p-aminophenol type for use in the present invention include N-methyl-p-aminophenol, p-aminophenol, and N-( ⁇ -hydroxyethyl)-p-aminophenol, N-(4-hydroxyphenyl)glycine.
  • N-methyl-p-aminophenol is preferred.
  • the developing agent is preferably used in a concentration of of 0.05 to 0.8 mol/liter.
  • a combination of a dihydroxybenzene and a 1-phenyl-3-pyrazolidone, or a combination of a dihydroxybenzene and a p-aminophenol is employed as the developing agent, it is desirable to use the former constituent in a concentration of 0.05 to 0.5 mol/liter, and the latter in a concentration of 0.06 mol/liter or less.
  • sulfite type preservative for use in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, formaldehyde adduct of sodium bisulfite, and the like.
  • a preferred concentration of sulfite ion is 0.20 mol/liter or more, and particularly 0.3 mol/liter or more. Since the sulfite precipitates when used in excess, a concentration upper limit of 1.2 mol/liter is practical.
  • Water-soluble inorganic alkali metal salts e.g., sodium hydroxide, sodium carbonate
  • the boric acid disclosed in JP-A-62-186259 can be used as a buffer.
  • the sugars disclosed in JP-A-60-93433 e.g., saccharose
  • oximes e.g., acetoxime
  • phenols e.g., 5-sulfosalicylic acid
  • tertiary phosphates e.g., sodium and potassium salts thereof
  • boric acid is preferred.
  • Buffers (preferably having an acid dissociation constant ranging from 1 ⁇ 10 ⁇ 11 to 3 ⁇ 10 ⁇ 13) can be added to the developer for use in the present invention in a concentration of 0.1 mol/liter or more, and particularly from 0.2 to 1 mol/liter.
  • the addition of such buffers enables the steady generation of the effects - provided by the hydrazine derivative, namely, a great increase in contrast and enhancement of sensitivity, irrespective of a silver coverage of the light-sensitive material and the photographic density, even when an automatic developing machine is used.
  • the above-described acid dissociation constant may be a first order, second order, third order or higher order dissociation, with the proviso that the buffer for use in the present invention has an acid dissociation constant of any order within the above-described range, namely, from 1 ⁇ 10 ⁇ 11 to 3 ⁇ 10 ⁇ 13.
  • the developer for use in the present invention may contain a pH buffer such as potassium hydroxide and sodium carbonate; a development inhibitor such as sodium bromide and potassium bromide; an organic solvent such as ethylene glycol, diethylene glycol, triethylene glycol and dimethylformamide; a development accelerator such as an alkanolamine including diethanolamine, triethanolamine and the like, imidazole and its derivatives; and an antifoggant or a black pepper inhibitor, such as a mercapto compound including 1-phenyl-5-mercaptotetrazole, and an indazole compound including 5-nitroindazole; and may optionally contain a toning agent, a surface active agent, a defoaming agent, a water softener, a hardener, etc.
  • a pH buffer such as potassium hydroxide and sodium carbonate
  • a development inhibitor such as sodium bromide and potassium bromide
  • an organic solvent such as ethylene glycol, diethylene glycol, triethylene glycol and dimethylformamide
  • the terminology “substantially free from benzotriazoles” means that benzotriazoles are contained in the developer in an amount of 35 mg/liter or less.
  • the fixing agent for use in the present invention contains a thiosulfate, e.g., sodium thiosulfate, ammonium thiosulfate or the like. From the standpoint of fixation speed, ammonium thiosulfate is preferred in particular.
  • the amount of the fixing agent generally ranges from about 0.1 to about 0.5 mol/liter.
  • Acid hardeners for use in a fixer which in accordance with the present invention include water-soluble aluminum salts, chromium salts, and an ethylenediaminetetraacetic acid complex utilizing a ferric compound as an oxidizing agent.
  • Preferred compounds include water-soluble aluminum salts, e.g., aluminum chloride, aluminum sulfate, and potassium alum.
  • Dibasic acids for use in the fixer include tartaric acid, a tartaric acid derivative, citric acid, a citric acid derivative, and mixtures of two or more thereof. These acids are effective when contained in a concentration of 0.005 mol/liter or more, particularly from 0.01 to 0.03 mol/liter.
  • tartaric acid potassium tartarate, sodium tartarate, potassium hydrogentartarate, sodium hydrogentartarate, potassium sodium tartarate, ammonium tartarate, ammonium potassium tartarate, aluminum potassium tartarate, antimonyl potassium tartarate, antimonyl sodium tartarate, lithium hydrogen-tartarate, magnesium hydrogentartarate, potassium boron tartarate, and potassium lithium tartarate, can be used effectively as the tartaric acid or derivatives thereof.
  • citric acid and its derivatives effective in the present invention include citric acid, sodium citrate, potassium citrate, lithium citrate, and ammonium citrate.
  • the fixer can contain preservatives (e.g., sulfites, hydrogen sulfites), pH buffers (e.g., acetic acid, boric acid), pH adjusters (e.g., sulfuric acid), and chelating agents, if desired.
  • pH buffers are used in an amount of about 10 to 40 g/liter, preferably about 18 to 25 g/liter, because the developer of the present invention has a high pH value.
  • the development and fixation are each carried out for a period of from 10 seconds to 1 minute at about 20°C to about 50°C.
  • a monodisperse cubic silver iodobromide emulsion (having a variation coefficient of 12%, an iodide content of 0.5 mol%, and a uniform distribution of iodide) was prepared using a controlled double jet method in the presence of ammonia.
  • K3IrCl6 was added in an amount of 5 ⁇ 10 ⁇ 7 mol per mol of Ag.
  • Emulsion (a) The emulsion was desalted using the flocculation process and maintained at 50°C, and thereto were added 5 ⁇ 10 ⁇ 4 mol/mol Ag of the sensitizing dye illustrated below and 10 ⁇ 3 mol/mol Ag of a KI solution. After the lapse of 15 minutes, 2 ⁇ 10 ⁇ 4 mol/mol Ag of 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene was further added, and then the emulsion was cooled. The thus obtained emulsion was designated as Emulsion (a).
  • Emulsion (a) To Emulsion (a) were added Hydrazine Compound I-15), Nucleation Accelerator (II-8), and 5-methylbenzotriazole in amounts of 2 ⁇ 10 ⁇ 4 mol/mol Ag, 8.6 ⁇ 10 ⁇ 3 mol/mol Ag and 3 ⁇ 10 ⁇ 3 mol/mol Ag, respectively. Furthermore, 1.0 g/m of polyethyl acrylate and 140 mg/m of 1,3-divinylsulfonyl-2-propanol as a hardener were added. The resulting emulsion was coated on a polyethylene terephthalate film to provide a silver coverage of 4.0 g/m.
  • a layer containing 1.2 g/m of gelatin, 40 mg/m of amorphous SiO2 having a grain size of about 3 ⁇ m as a matting agent, 0.1 g/m of methanolsilica, the fluorine-containing surface active agent of the structural formula and sodium dodecylbenzenesulfonate as a coating aid were coated as protective layer over the emulsion layer.
  • the thus prepared sensitive material was designated as Photosensitive Material A.
  • Photosensitive Material A was evaluated with regard to spread and copy dot qualities according to the methods described below.
  • a backing layer was coated having the following composition.
  • a transmission portrait made up of dots and a step wedge having stepwise changed dot area percentages were prepared using a monochromatic scanner SCANART 30 and the photosensitive material SF-100, both produced by Fuji Photo Film Co., Ltd.
  • the screen ruling therein was 150 lines/inch.
  • the foregoing original was set in a process camera C-440, produced by Dainippon Screen Mfg. Co., Ltd., such that the image thereon might be spread to the size of equimultiple, and then the sample to be evaluated was irradiated of the transmission portrait with an Xe lamp.
  • the exposure was carried out such that the halftone dots in the original corresponding to the 95% portion of the step wedge were converted into images having a dot area percentage of 5%.
  • the gradation reproducibility of the shadow part of the sample was evaluated in five grades (from 5 to 1, 5 being the best, 1 being the worst, 3 indicating that the halftone dots are somewhat distorted, but acceptable for practical use).
  • a step wedge having stepwise changed dot area percentages was prepared using a monochromatic scanner SCANART 30 and the paper SP-100 wp, both produced by Fuji Photo Film Co., Ltd. A screen ruling of 150 lines/inch was employed upon exposure.
  • the original and the sample to be evaluated were set in their respective prescribed positions of a process camera C-690 (Autocompanica with a xenon light source), produced by Dainippon Screen Mfg. Co., Ltd., and the photographing was carried out by irradiation of the reflection original with a Xe lamp.
  • a process camera C-690 Autocompanica with a xenon light source
  • the exposure time was adjusted such that the area corresponding to the 80% part of the step wedge on the original corresponded to 10% on the sample.
  • the gradation reproducibility of the shadow part of the sample was evaluated in five grades ("5" indicates the best quality, and "1" indicates the poorest quality).
  • the exposure time required for converting the original to be spread corresponding to the 95% part of the step wedge into a 5% part on a sample to be tested was determined.
  • the sensitivity is shown below as a relative value, with Comparative Sample (1) being taken as 100.
  • the exposure time required for converting the copy dot original corresponding to the 80% part of the step wedge into a 10% part on a sample to be tested was determined.
  • the sensitivity is shown below as a relative value, with Comparative Sample (1) being taken as 100.
  • Emulsion (a) prepared in Example 1 were added 2 ⁇ 10 ⁇ 5 mol/mol Ag of Hydrazine Compound I-19) used in the present invention, and a dispersion of 1.0 g/m of polyethyl acrylate, and 0.14 g/m of a hardener, 1,3-divinylsulfonyl-2-propanol.
  • the resulting emulsion was coated on a polyethylene terephthalate film to provide a silver coverage of 4.0 g/m, and thereon was coated the same protective layer as in Example 1.
  • the thus obtained photosensitive material was designated as Photosensitive Material B.
  • Photosensitive Material B was processed in the same manner as in Example 1, except that the following Developers (4) and (5) were used, and the development condition was 34°C for 30 seconds. The thus processed samples were evaluated with respect to spread and copy dot quality. The results are shown in Table 2.
  • Comparative Sample 1 corresponds to that disclosed in JP-A-53-66732.
  • Example 3 Similar to the results obtained in Example 1, Developer (3) used in accordance with the present invention provided higher sensitivity and better image quality than Developer (1). Moreover, the presence of the dye contributed to a further improvement in image quality as compared with Example 1. The extent of the improvement was greater in the case where Developer (3) was used than in the case where Developer (1) was used.
  • a monodisperse cubic silver iodobromide emulsion having an average grain size of 0.25 ⁇ m (variation coefficient: 12%, a silver iodide content: 0.5 mol%, and iodide distribution: uniform) was prepared using a controlled double jet method.
  • K3IrCl6 was added in an amount of 4 ⁇ 10 ⁇ 7 mol per mol of Ag.
  • the emulsion was desalted using the flocculation process and was maintained at 50°C, and thereto were added 5 ⁇ 10 ⁇ 4 mol/mol Ag of the sensitizing dye illustrated below and 10 ⁇ 3 mol/mol Ag of a KI solution. After the lapse of 15 minutes, the emulsion was cooled.
  • the hydrazine compound illustrated below was added to provide a coverage of 10 mg/m:
  • Example 1 a backing layer was coated as in Example 1.
  • the exposure time required for converting the part of the original to be spread corresponding to the 95% part of the step wedge to the 5% part on a sample to be tested was determined.
  • the sensitivity is shown below as a relative value, with Sample (1) being taken as 100.
  • the exposure time required for converting the part of the copy dot original corresponding to the 80% part of the step wedge to the 10% part on a sample to be tested was determined.
  • the sensitivity is shown below as a relative value, with Sample (1) being taken as 100.
  • the developer having the composition below as used.
  • Formula of Developer Hydroquinone 25.0 g 4-Methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidone 0.5 g Potassium Sulfite 90.0 g Disodium Ethylenediaminetetraacetate 2.0 g Potassium Bromide 5.0 g 2-Mercaptobenzimidazole-5-sulfonic Acid 0.3 g Sodium Carbonate 50.0 g NaOH added in an amount needed to adjust the pH to 10.7 Water to make 1 liter
  • Samples were prepared in the same manner as Sample (2) in Example 3, except that the hydrazine compound incorporated therein was replaced by the exemplified Compounds I-18), I-19) and I-41), as indicated in Table 5.
  • the hydrazine compounds were added in the amounts indicated in Table 5. Furthermore, Dye D-1 was added to each sample to provide a coverage of 100 mg/m. The samples were processed and evaluated in the same manner as in Example 3.
  • the comparative sample which did not contain a hydrazine compound was quite inferior in sensitivity and image quality.

Landscapes

  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)

Claims (8)

  1. Verfahren zur Bildung eines Schwarz-Weiß-Bildes mit sehr hohem Kontrast mit einem Gammawert von 8 oder höher, unter Verwendung eines lichtempfindlichen bildweise belichteten Negativmaterials, umfassend einen Träger mit wenigstens einer darauf angeordneten hydrophilen Kolloidschicht, wobei wenigstens eine Schicht davon eine Silberhalogenidemulsionsschicht ist und wenigstens eine hydrophile Kolloidschicht ein durch die Formel (I) dargestelltes Hydrazinderivat enthält, umfassend das Verarbeiten des lichtempfindlichen Materials mit einem Entwickler mit einem pH von 11,2 oder weniger, wobei der Entwickler Benzotriazole in einer Menge von weniger als 35 mg/l und kein 1-Phenyl-s-mercaptotetrazol
    Figure imgb0175
     enthält, worin bedeuten: R₁ eine aliphatische Gruppe oder eine aromatische Gruppe; R₂ ein Wasserstoffatom, eine Alkylgruppe, eine Arylgruppe, eine Alkoxygruppe, eine Aryloxygruppe, eine Aminogruppe, eine Carbamoylgruppe oder eine Oxycarbonylgruppe; G₁ eine Carbonylgruppe, eine Sulfonylgruppe, eine Sulfoxygruppe,
    Figure imgb0176
     oder eine Iminomethylengruppe; und jedes A₁ und A₂ ein Wasserstoffatom oder eines von A₁ und A₂ ein Wasserstoffatom und das andere eine Alkylsulfonylgruppe, eine Arylsulfonylgruppe oder eine Acylgruppe.
  2. Verfahren nach Anspruch 1, worin das lichtempfindliche Material wenigstens einen Farbstoff mit einem Absorptionsmaximum im Wellenlängenbereich von 300 bis 420 nm besitzt.
  3. Verfahren nach Anspruch 1, worin wenigstens eine hydrophile Kolloidschicht wenigstens einen Keimbildungsbeschleuniger enthält, ausgewählt aus den durch die Formeln (II) und (III) dargestellten Verbindungen:

            Y-[(X)n-A-B]m     (II)

    worin bedeuten: Y eine Gruppe, welche auf Silberhalogenid adsorbiert; X ein Wasserstoffatom oder eine zweiwertige Verknüpfungsgruppe; A eine zweiwertige Verknüpfungsgruppe; B eine Aminogruppe, eine Ammoniumgruppe oder eine Stickstoff-enthaltende heterocyclische Gruppe; m 1, 2 oder 3; und n 0 oder 1;
    Figure imgb0177
     worin bedeuten: R¹ und R jeweils ein Wasserstoffatom oder einen aliphatischen Rest, oder R¹ und R bilden durch Kombination einen Ring; R³ eine zweiwertige aliphatische Gruppe; X eine zweiwertige, Stickstoff-, Sauerstoff- oder Schwefel-enthaltende heterocyclische Gruppe; n 0 oder 1; und M ein Wasserstoffatom, ein Alkalimetall, ein Erdalkalimetall, ein quaternäres Ammoniumsalz, ein quaternäres Phosphoniumsalz oder eine Amidinogruppe.
  4. Verfahren nach Anspruch 1, worin das Hydrazinderivat zu einer Flächeneinheit des lichtempfindlichen Materials in einer Menge von 1 x 10⁻⁶ Mol bis 5 x 10⁻ Mol pro Mol Silberhalogenid zugegeben wird.
  5. Verfahren nach Anspruch 2, worin der wenigstens eine Farbstoff mit einem Absorptionsmaximum im Wellenlängenbereich von 300 nm bis 420 nm in einer Menge von 10⁻g/m to 1 g/m des lichtempfindlichen Materials zugegeben wird.
  6. Verfahren nach Anspruch 3, worin der wenigstens eine Keimbildungsbeschleuniger, ausgewählt aus den Verbindungen, dargestellt durch die Formeln (II) und (III), zugegeben wird in einer Menge von 1,0 x 10⁻³ bis 0,5 g/m des lichtempfindlichen Materials.
  7. Verfahren nach Anspruch 1, worin der Entwickler ein stabiler Entwickler ist, welcher wenigstens 0,2 Mol/Liter Sulfitionen als Haltbarkeitsmittel enthält.
  8. Verfahren nach Anspruch 1, worin der Entwickler einen pH von 11,0 bis 9,5 besitzt.
EP90108809A 1989-05-10 1990-05-10 Verfahren zur Bildherstellung Expired - Lifetime EP0397167B1 (de)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP1116832A JPH02294637A (ja) 1989-05-10 1989-05-10 画像形成法
JP116833/89 1989-05-10
JP116832/89 1989-05-10
JP1116833A JP2887367B2 (ja) 1989-05-10 1989-05-10 画像形成方法

Publications (3)

Publication Number Publication Date
EP0397167A2 EP0397167A2 (de) 1990-11-14
EP0397167A3 EP0397167A3 (de) 1991-01-23
EP0397167B1 true EP0397167B1 (de) 1996-03-13

Family

ID=26455069

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90108809A Expired - Lifetime EP0397167B1 (de) 1989-05-10 1990-05-10 Verfahren zur Bildherstellung

Country Status (2)

Country Link
EP (1) EP0397167B1 (de)
DE (1) DE69025793T2 (de)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0316864A2 (de) * 1987-11-17 1989-05-24 Konica Corporation Lichtempfindliches photographisches Silberhalogenidmaterial und Verfahren zur Behandlung

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS589412B2 (ja) * 1977-08-30 1983-02-21 富士写真フイルム株式会社 ハロゲン化銀写真感光材料の現像方法
US4269929A (en) * 1980-01-14 1981-05-26 Eastman Kodak Company High contrast development of photographic elements
JPS60200250A (ja) * 1984-03-23 1985-10-09 Fuji Photo Film Co Ltd 高コントラストネガ画像形成方法
JP2604154B2 (ja) * 1987-05-19 1997-04-30 富士写真フイルム株式会社 ハロゲン化銀写真感光材料
DE68926687T2 (de) * 1988-01-11 1997-03-06 Fuji Photo Film Co Ltd Verfahren zur Erzeugung von extrem hochkontrastreichen negativen Bildern

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0316864A2 (de) * 1987-11-17 1989-05-24 Konica Corporation Lichtempfindliches photographisches Silberhalogenidmaterial und Verfahren zur Behandlung

Also Published As

Publication number Publication date
EP0397167A3 (de) 1991-01-23
DE69025793D1 (de) 1996-04-18
EP0397167A2 (de) 1990-11-14
DE69025793T2 (de) 1996-10-17

Similar Documents

Publication Publication Date Title
US5139921A (en) Process for forming super high contrast negative images
EP0292986B1 (de) Photographische Silberhalogenidmaterialien
US5230983A (en) Silver halide photographic material
US5288590A (en) High-contrast silver halide photographic material and method for forming an image with the same
US5200298A (en) Method of forming images
US5447835A (en) Silver halide photographic material containing hydrazine compounds
EP0393720A2 (de) Photographische Silberhalogenidmaterialien
EP0324426B1 (de) Verfahren zur Erzeugung von extrem hochkontrastreichen negativen Bildern
EP0228084B1 (de) Verfahren zur Herstellung eines Bildes
EP0539925A1 (de) Photographisches lichtempfindliches Silberhalogenidmaterial
JPH0862759A (ja) ハロゲン化銀写真感光材料およびそれを用いた画像形成方法
US4435500A (en) Method for developing silver halide photographic light-sensitive material
US4873173A (en) Method of forming image providing a change in sensitivity by altering the pH of the developer
US5085970A (en) Image forming method
JP2757063B2 (ja) ハロゲン化銀写真感光材料
EP0398355B1 (de) Photographisches Silberhalogenidmaterial
US5238780A (en) Method of image formation
EP0393721B1 (de) Photographisches Silberhalogenidmaterial
JPH0816777B2 (ja) 画像形成方法
US5278025A (en) Method for forming images
US5187058A (en) Silver halide photographic material
EP0397167B1 (de) Verfahren zur Bildherstellung
US5153098A (en) Image forming method
EP0556845B1 (de) Verfahren zum Verarbeiten eines photographischen Silberhalogenidmaterials
JPH07295165A (ja) ハロゲン化銀写真感光材料の処理方法

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): DE GB

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): DE GB

17P Request for examination filed

Effective date: 19910318

17Q First examination report despatched

Effective date: 19940722

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE GB

REF Corresponds to:

Ref document number: 69025793

Country of ref document: DE

Date of ref document: 19960418

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20090420

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20090506

Year of fee payment: 20

REG Reference to a national code

Ref country code: GB

Ref legal event code: PE20

Expiry date: 20100509

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20100509

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20100510