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, halftone photographs and the like, such that the original contains a mixture of images differing in density and line width.
• 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 systems 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.
• 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.
• a method of forming a black-and-white image of very high contrast having a gamma value of 8 or more using a negative imagewise exposed photosensitive material comprising a support having thereon at least one hydro­philic colloid layer, at least one layer of which is a silver halide emulsion layer, at least one of said hydro­philic colloid layer containing a hydrazine derivative represented by formula (I), comprising processing the photosensitive material with a developer having a pH of 11.2 or lower, said developer being substantially free from benzotriazoles: wherein R1 represents an aliphatic group or an aromatic group; R2 represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group, a carbamoyl group or an oxycarbonyl group; G1 represents a carbonyl group, a sulfonyl group, a sulfoxy group, or an iminomethylene
• 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 carbonamido 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 naphthalene 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.
• straight chain, branched or cyclic alkyl groups especially those containing from 1 to 20 carbon atoms
• 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 forma­ tion 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.
• p represents 0 or 1
• q is 2
• p repre­ sents 0 or 1
• p represents 0 or 1.
• CR c 1R 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 acy
• 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 U.S.
• 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 of 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 ⁇ 2 mol, and particularly preferably from 1 ⁇ 10 ⁇ 5 to 2 ⁇ 10 ⁇ 2 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 preferively 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, etc. 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.
• R ⁇ 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.
• a mordant it is desirable that the dye be present in an emulsion layer or a layer located outside of the emulsion layer.
• 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"), U.S. Patents 2,548,564, 2,882,156 and 3,444,138, etc.
• 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 ⁇ 2 g/m2 to 1 g/m2, and preferably from 50 mg/m2 to 500 mg/m2 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),
• divalent linkage group repre­sented by X examples 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 R12 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 R12 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 R12 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 atom
• 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 R12 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 R2 each represents a hydrogen atom, or an aliphatic group, or R1 and R2 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 R2 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.,
• Groups which are particularly preferred as R1 and R2 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.
• 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/m2, and preferably from 5.0 ⁇ 10 ⁇ 3 to 0.3 g/m2.
• 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, etc.). 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 of 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, chloropalladates and the like 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, silver nitrate, etc.
• 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, pyridine and like nuclei; 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, quinoline and like nuclei.
• 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-thio­oxazolidine-2,4-dione, thiazolidine-2,4-dione, rhodanine, thiobarbituric acid and like nuclei, as ketomethylene structure-containing nuclei.
• 5- or 6-membered heterocyclic nuclei such as pyrazoline-5-one, thiohydantoin, 2-thio­oxazolidine-2,4-dione, thiazolidine-2,4-dione, rhodanine, thiobarbituric acid and like nuclei, as ketomethylene structure-containing nuclei.
• 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 ⁇ 2 mol, per mole of silver.
• the photographic material of 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, etc.; mercaptopyrimidines; mercapto­triazines; thioketo compounds such as oxazolidinethiones; azaindenes such as triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a,7)tetra­azaindenes), pentaazaindenes, etc.; and compounds which are known as antifoggant or stabilizers, such as benzene­thio
• 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 of 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), mucohalogenic acids, etc.
• 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
• mucohalogenic acids etc.
• 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 U.S. Patent 3,325,287 are preferred.
• the photographic emulsion layers and other hydrophilic colloid layers of the photographic material of 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), etc.
• 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 U.S. Patent 4,201,586 and JP-A-60-80849, for example, are especially preferred.
• the photographic emulsion of 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, etc., alone or in combination thereof, or in combination with repeating units derived from acrylic acid, methacrylic acid, etc.
• the photographic light-sensitive material of 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 of 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, ascorbic acid, etc., and homopolymers and copolymers having constituent repeating units derived from an acid monomer such as acrylic acid, maleic acid, phthalic acid, etc.
• organic acids such as salicylic acid, acetic acid, ascorbic acid, etc.
• homopolymers and copolymers having constituent repeating units derived from an acid monomer such as acrylic acid, maleic acid, phthalic acid, etc.
• 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 of the present invention can include hydrophilic colloid layers such as a surface protecting layer, an interlayer, a filter layer, an antihalation layer, etc., in addition to a silver halide emulsion layer.
• the light-sensitive material of 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 of the present invention can contain a matting agent such as methyl methacrylate homopolymer, methyl methacrylate-­methacrylic acid copolymer, magnesium oxide, etc., and a slipping agents such as a silicone compound disclosed in U.S. Patents 3,489,576 and 4,047,958, colloidal silica disclosed in JP-B-56-23139, paraffin wax, higher fatty acid esters, starch, etc.
• a matting agent such as methyl methacrylate homopolymer, methyl methacrylate-­methacrylic acid copolymer, magnesium oxide, etc.
• a slipping agents such as a silicone compound disclosed in U.S. Patents 3,489,576 and 4,047,958, colloidal silica disclosed in JP-B-56-23139, paraffin wax, higher fatty acid esters, starch, etc.
• 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 of 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 dihydroxybenzenes For good developability, the combined use of dihydroxy­benzenes and 1-phenyl-3-pyrazolidones, or the combined use of dihydroxybenzenes and p-aminophenols is preferivelyable.
• 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, 1-phenyl-4-methyl-­4-hydroxymethyl-3-pyrazolidone, etc.
• Developing agents of p-aminophenol type for use in the present invention include N-methyl-p-aminophenol, p-aminophenol, N-( ⁇ -hydroxyethyl)-p-aminophenol, N-(4-­hydroxyphenyl)glycine, etc.
• 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 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), and the like can be used as a buffer.
• 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, etc.; 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 di
• 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 ethylene-­diaminetetraacetic acid complex utilizing a ferric compound as an oxidizing agent.
• Preferred compounds include water-soluble aluminum salts, e.g., aluminum chloride, aluminum sulfate, potassium alum and the like.
• 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 hydrogen­tartarate, magnesium hydrogentartarate, potassium boron tartarate, potassium lithium tartarate, etc.
• 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 hydrogen­tartarate, magnesium hydrogentartarate, potassium boron tartarate, potassium lithium tartarate, etc.
• citric acid and its derivatives effective in the present invention include citric acid, sodium citrate, potassium citrate, lithium citrate, ammonium citrate and so on.
• 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/m2 of polyethyl acrylate and 140 mg/m2 of 1,3-divinylsulfonyl-2-propanol as a hardener were added. The resulting emulsion was coated on a poly­ ethylene terephthalate film to provide a silver coverage of 4.0 g/m2.
• a layer containing 1.2 g/m2 of gelatin, 40 mg/m2 of amorphous SiO2 having a grain size of about 3 ⁇ m as a matting agent, 0.1 g/m2 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 reproduci­ bility 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) of the present invention, and a dispersion of 1.0 g/m2 of polyethyl acrylate, and 0.14 g/m2 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/m2, 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.
• Composition of Developer : (4) (5) Hydroquinone 50.0 g " N-Methyl-p-aminophenol 0.3 g " 5-Sulfosalicylic Acid 30 g " Boric Acid 20 g " Potassium Sulfite 110 g " Disodium Ethylenediaminetetraacetate 1.0 g " KBr 10.0 g " 5-Methylbenzotriazole 0.4 g - 2-Mercaptobenzimidazole-5-sulfonic Acid 0.3 g " Sodium 3-(5-Mercaptotetrazole)benzenesulfonate 0.2 g " 6-Dimethylamino-1-hexanol 4.0 g " Sodium Toluenes
• Comparative Sample 1 corresponds to that disclosed in JP-A-53-66732.
• Developer (3) 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/m2:
• 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/m2. 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.

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• 1990
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