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
  • 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

• an image forming system having super high contrast (in particular, a gamma ( G) of at least 10) is required for improving the reproduction of continuous tone by dot images or the reproduction of line images.
• lith developer For this purpose, a specific developer called “lith developer” has hitherto been used.
• the lith developer consists of hydroquinone as the developing agent and also contains a sulfite as a preservative in the form of an addition product with formaldehyde, whereby the concentration of free sulfite ions is reduced as low as possible (typically below 0.1 moliliter). Accordingly, the lith developer is susceptible to air-oxidation and thus cannot be stored for over 3 days.
• the pH of the developer must be at least 11.0.
• the developing agent is liable to be oxidized, the pH is liable to deviate by absorbing C0 2 from the air and stable photographic properties are thus not obtained. Accordingly, a process of obtaining super high contrast images in a developer having a high sulfite ion concentration at a pH below 11.0 has been desired.
• JP-A-61-167939 the term "JP-A” as used herein mean as "unexamined pubiished Japanese patent application”
• disulfide compounds in JP-A-61-198147 the term "JP-A” as used herein mean as "unexamined pubiished Japanese patent application”
• amine series compounds in JP-A-60-140340 are disclosed as contrast enhancing agents.
• a low-speed, light-sensitive material for safelight use employing a hydrazine compound, and containing a water-soluble rhodium salt, is disclosed in JP-A-60-83038 and 60-162246.
• the addition of a sufficient amount of rhodium salt to increase the sensitivity obstructs the increase of contrast by the hydrazine compound, whereby the desired sufficiently high contrast images are not obtained.
• An object of this invention is to provide a process of forming super high contrast images using a developer having a pH of from 9.6 to 11.0 in a system containing a hydrazine compound.
• Another object of this invention is to provide a process of forming super high contrast images with stable photographic performance using a stable developer.
• a process for forming super high contrast negative images comprises the steps of: processing a super high contrast negative-type silver halide photographic material comprising a support having formed thereon at least one layer, one of which must be a silver halide emulsion layer, containing therein or in another hydrophilic colloid layer at least one hydrazine derivative and at least one nucleation accelerator represented by formula (la) or (Ib) with a developer having a pH of from 9.6 to 11.0; Y[(A 1 ) p A 2 -B] m (la) M 1 S(X) n A 3 -B (Ib) wherein Y represents a group adsorbing onto silver halide; A 1 represents a divalent linkage group composed of an atom or an atomic group selected from hydrogen, carbon, nitrogen, oxygen, and sulfur; A 2 represents a divalent linkage; A3 represents a divalent linkage group composed of an atom or an atomic group selected from carbon
• Y represents a group which adsorbs onto silver halide as, for example, a nitrogen-containing heterocyclic group.
• the compound of formula (la) is shown by formula (II) wherein t represents 0 or the integer 1; [(A 1 ) p A 2 -B] m has the same meaning as in formula (la) described above; and Q represents an atomic group necessary for forming a 5-or 6-membered heterocyclic ring composed of members selected from carbon, nitrogen, oxygen, and sulfur.
• the heterocyclic ring may be condensed with a carbon aromatic ring or a heteroaromatic ring.
• heterocyclic ring formed by Q examples include the indazoles, benzimidazoles, benzotriazoles, benzoxazoles, benzthiazoles, imidazoles, thiazoles, oxazoles, triazoles, tetrazoles, azaindenes, pyrazoles, indoles, triazines, pyrimidines, pyridines, and quinolines. These heterocyclic rings may be substituted as indicated below.
• M 2 represents a hydrogen atom, an alkali metal atom (e.g., sodium and potassium), an ammonium group (e.g., trimethylammonium and dimethylbenzylammonium), or a group capable of being replaced with hydrogen or an alkali metal atom under alkali conditions (e.g., acetyl, cyanoethyl, and methanesulfonylethyl).
• an alkali metal atom e.g., sodium and potassium
• an ammonium group e.g., trimethylammonium and dimethylbenzylammonium
• a group capable of being replaced with hydrogen or an alkali metal atom under alkali conditions e.g., acetyl, cyanoethyl, and methanesulfonylethyl.
• these heterocyclic rings may be substituted by a nitro group, a halogen atom (e.g., chlorine and bromine), a mercapto group, a cyano group, a substituted or unsubstituted alkyl group (e.g., methyl, ethyl, propyl, t-butyl cyanoethyl, methoxyethyl, and methylthioethyl), a substituted or unsubstituted aryl group (e.g., phenyl, 4-methanesulfonamidophenyl, 4-methylphenyl, 3,4-dichlorophenyl, and naphthyl), a substituted or unsubstituted alkenyl group (e.g., allyl), a substituted or unsubstituted aralkyl group (e.g., benzyl, 4-methylbenzyl, and phenethyl), a substituted or
• Examples of the divalent linkage group shown by A 1 include:
• R 1 , R 2 , R 3 , R 4 , Rs, R 6 , R 7 , R 8 , R 3 , and R 10 each represents a hydrogen atom, a substituted or unsubstituted alkyl group (e.g., methyl, ethyl, propyl, and n-butyl), a substituted or unsubstituted aryl group (e.g., phenyl and 2-methylphenyl), a substituted or unsubstituted alkenyl group (e.g., propenyl and 1-methylvinyl), or a substituted or unsubstituted aralkyl group (e.g., benzyl and phenethyl).
• a substituted or unsubstituted alkyl group e.g., methyl, ethyl, propyl, and n-butyl
• a substituted or unsubstituted aryl group e.g.,
• the above divalent structures may be further combined with a straight chain or branched alkylene group preferably having to 1 to 6 carbon atoms and more preferably 1 to 3 carbon atoms (e.g., methylene, ethylene, propylene, butylene, hexylene, and 1-methylethylene) to also comprise A, ,
• a 2 represents a divalent linkage group such as a straight chain or branched alkylene group (e.g., methylene, ethylene propylene, butylene, hexylene, and 1-methylethylene), a straight chain or branched alkenylene group (e.g., vinylene and 1-methylvinylene), a straight chain or branched aralkylene group (e.g., benzylidene), a straight chain or branched arylene group (e.g., phenylene and naphthylene), etc.
• a straight chain or branched alkylene group e.g., methylene, ethylene propylene, butylene, hexylene, and 1-methylethylene
• a straight chain or branched alkenylene group e.g., vinylene and 1-methylvinylene
• a straight chain or branched aralkylene group e.g., benzylidene
• arylene group e.g
• a 1 and A 2 in formula (11) may be further substituted with the groups represented by A 1 and A z .
• R 11 and R 22 which may be the same or different, each represents a hydrogen atom, a substituted or unsubstituted alkyl, alkenyl group or aralkyl group having from 1 to 30 carbon atoms and these groups may be straight chain groups (e.g., methyl, ethyl, n-propyl, n-butyl, n-octyl, allyl, 3-butenyl, benzyl, and 1-naphthylmethyl), branched groups (e.g., iso-propyl and t-octyl), or cyclic groups (e.g., cyclohexyl).
• R 11 and R 22 which may be the same or different, each represents a hydrogen atom, a substituted or unsubstituted alkyl, alkenyl group or aralkyl group having from 1 to 30 carbon atoms and these groups may be straight chain groups (e.g., methyl, ethy
• R 11 and R 12 may combine with each other to form a ring which may contain at least one hetero atom e.g., oxygen, sulfur and nitrogen) so as to form a saturated heterocyclic ring such as pyrrolidyl, piperidyl, morpholino, etc.
• a hetero atom e.g., oxygen, sulfur and nitrogen
• substituents for R" and R 12 include a carboxy group, a sulfo group, a cyano group, a halogen atom (e.g., fluorine, chlorine, and bromine), a hydroxy group, an alkoxycarbonyl group having from 1 to 20 carbon atoms (e.g., methoxycarbonyl, ethoxycarbonyl, phenoxycarbonyl, and benzyloxycarbonyl), an alkoxy group having from 1 to 20 carbon atoms (e.g., methoxy, ethoxy, benzyloxy, and phenetyloxy), an aryloxy group having not more than 20 carbon atoms (e.g., phenoxy and p-tolyloxy), an acyloxy group having not more than 20 carbon atoms (e.g., acetyloxy and propionyloxy), an acyl group having not more than 20 carbon atoms (e.g., acetyl,
• the ammonium group shown by B is generally shown by formula (VIII).
• R 13 , R 14 , and R 15 have the same meaning as R 11 and R 12 in formula (VII) as described above and Z e represents an anion such as halide ion (e.g., Cl e , Br e and I e ) a sulfonate ion (e.g., trifluoromethanesulfonate ion, p-toluenesulfonate ion, benzenesulfonate ion, and p-chlorobenzenesulfonate ion), a sulfate ion (e.g., ethyl sulfate ion and methyl sulfate ions), a prechlorate ion, a tetrafluoroborate ion, etc.
• q represents the integer 0 or 1 and when the compound forms an intramolecular salt
• B is a 5- or 6-membered ring containing at least one nitrogen atom and the ring may have substituents or may be condensed with another ring.
• the nitrogen containing heterocyclic ring are an imidazolyl ring, a pyridyl ring, and a thiazolyl ring.
• the substituent for the amino group can be selected from the aforesaid substituents for R 11 and R 12 in formula (VII). At least one of Zi, Z 2 , and Z 3 must have the same meaning as (A 1 ) p A 2 -B.
• heterocyclic rings may be substituted by the substituents applied to the heterocyclic ring shown by Q in formula (II) as described above.
• the heterocyclic ring shown by X in formula (Ib) described above is a 5- or 6-membered heterocyclic ring containing at least one of nitrogen, oxygen, selenium, and sulfur and may be condensed with a carbon aromatic ring or a hetero aromatic ring.
• the heterocyclic ring is preferably aromatic and examples thereof are tetrazole, triazole, thiadiazole, oxadiazole, selenadiazole, imidazole, thiazole, oxazole, benzimidazole, benzthiazole, benzoxazole, benzselenazole, and pyrimidine. Among them, tetrazole and thiazole are particularly preferred.
• heterocyclic rings may be substituted by the same substituents applied to the heterocyclic rings shown by Q in formula (II).
• the linkage group shown by A3 may further comprise a linkage group by combinations of A 1 , A 2 and/or an alkinylene group ,
• the alkali metal shown by M 1 in formula (Ib) includes Na + , K + , Li + , etc.
• the alkaline earth metal shown by M includes Ca , Mg , etc.
• the quaternary ammonium salt shown by M 1 has from 4 to 30 carbon atoms and examples thereof include, (CH 3 ) 4 N ⁇ , (C 2 H 5 ) 4 N ⁇ , (C 4 H 9 ) 4 N ⁇ , C 6 H 5 CH 2 N ⁇ (CH 3 ) 3 , and C 16 H 33 N ⁇ (CH 3 ) 3 .
• examples of the quaternary phosphonium salt include (C 4 H 9 ) 4 P ⁇ , C 16 H 33 P ⁇ (CH 3 ) 3 , and C 6 H 5 CH 2 P ⁇ (CH 3 ) 3 .
• the group shown by Mi which can be replaced with hydrogen or an alkali metal atom under alkali conditions include an acetyl group, a cyanoethyl group, a methanesulfonylethyl group, etc.
• nucleation accelerators shown by formulae (Ia) and (Ib) are readily synthesized by the methods described in Berichte der Deutschen Chemischen Deutschen Chemischen Deutschen, 28, 77(1895), ibid., 22, 568 (1889), ibid., 29, 2483(1896), Journal of Chemical Society, 1932, 1806, Journal of The American Chemical Society, 71, 4000-(1949), Advances in Heterocyclic Chemistry, 9, 165(1968), Organic Synthesis, IV, 569(1963), Journal of The American Chemical Society, 45, 2390(1923), Chemische Berichte, 9, 465(1976), JP-A-50-37436 and JP-A-51-3231, U.S.
• Patents 3,295,976, 3,376,310, 2,585,388, and 2,541,924, JP-B-40-28496, JP-B-43-41353, JP-B-60-29390, JP-B-60-29391, JP-B-60-133061, and JP-B-61-1431 (the term "JP-B” as used herein means an "examined published Japanese patent application")
• JP-A-50-89034 JP-A-57-202531, JP-A-57-167023, JP-A-57-164735, JP-A-60-80839, JP-A-58-152235, JP-A-57-14836, JP-A-59-162546, JP-A-60-130731, JP-A-60-138548, JP-A-58-83852, JP-A-58-159529, JP-A-59-159162, JP-A-60-217358, and JP-A-61-80238.
• These accelerators may be used singly or in combination thereof.
• the hydrazine derivative for use in the present invention includes those having a sulfinyl group as described in U.S. Patent 4,478,928 and the compound shown by formula (IX).
• R 2 -NHNH-CHO (IX) wherein R 2 represents an aliphatic group or an aromatic group.
• the aliphatic group shown by R 21 in formula (IX) is preferably an aliphatic group having from 1 to 30 carbon atoms.
• a straight chain, branched, or cyclic alkyl group having from 1 to 20 carbon atoms is preferred.
• the branched alkyl group may be cyclized so as to form a saturated heterocyclic ring containing at least one hetero atom.
• the aforesaid alkyl group may have a substituent such as an aryl group, an aikoxy group, a sulfoxy group, a sulfonamido group, a carbonamido group, etc.
• Examples thereof are t-butyl, n-octyl, t-octyl, cyclohexyl, pyrrolidyl, imidazolyl, tetrahydrofuryl, and morpholino.
• the aromatic group shown by R 21 in formula (IX) is a monocyclic or dicyclic aryl group or an unsaturated heterocyclic group.
• the unsaturated heterocyclic group may be condensed with a monocyclic or dicyclic aryl group to form a heteroaryl group.
• Examples thereof are 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.
• the groups having a benzene ring are preferred.
• R 21 is a particularly preferred aryl group.
• the aryl group or aromatic group shown by R 21 may be substituted.
• substituents include a straight chain, branched, or cyclic alkyl group (preferably having from 1 to 20 carbon atoms), an aralkyl group (preferably a monocyclic or dicyclic ring the alkyl moiety of which has from 1 to 3 carbon atoms), an alkoxy group (preferably having from 1 to 20 carbon atoms), a substituted amino group (preferably an amino group substituted by an alkyl group having from 1 to 20 carbon atoms), an acylamino group (preferably having from 2 to 30 carbon atoms), a sulfonamido group (preferably having from 1 to 30 carbon atoms) and a ureido group (preferably having from 1 to 30 carbon atoms).
• R 21 in formula (IX) may have therein a ballast group being usually used to immobilize photographic additives such as couplers, etc.
• the ballast group is a group having at least 8 carbon atoms and is relatively inert to photographic properties. Examples thereof include an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group, and an alkylphenoxy group.
• R 21 in formula (IX) may have therein a group for enhancing the adsorption onto the surface of silver halide grains.
• adsorptive groups include a thiourea group, a heterocyclic thioamido group, a mercaptoheterocyclic group, a triazole group, etc., as disclosed in U.S. Patent 4,385,108.
• particularly preferred compounds of formula (IX) have therein a group which enhances adsorption onto the surface of silver halide grains.
• Such adsorptive groups include a thiourea group, a heterocyclic thioamido group, a mercaptoheterocyclic group, a triazole group, etc. as disclosed in U.S. Patent 4,385,108.
• the preferred substituents for the aryl group or aromatic group shown by R 1 include an amido group, a ureido group, a thiourea group, etc.
• a sulfonamido group is particularly preferred.
• the nucleation accelerator and the hydrazine derivative of the present invention are preferably incorporated in a silver halide emulsion layer, but they may also be incorporated in other light-insensitive hydrophilic colloid layers (e.g., protective layer, interlayer, filter layer, antihalation layer, etc.), preferably those adjacent to a silver halide emulsion layer. They may be added in the same layer or different layers.
• Water soluble compound of formulae (la), (Ib) and (IX) may be added to the hydrophilic colloid solution as an aqueous solution thereof. Conversly, when the compound is sparingly soluble in water, the compound may be added thereto as a solution in an organic solvent which is miscible with water.
• solvent examples include water, methanol, ethanol, acetone, dimethylformamide, methylcellosolve, etc.
• the optimal amount of the compounds of formula (la), (Ib) and (IX) are selected according to the grain size and the halogen composition of the silver halide emulsion, the method and extent of chemical sensitization, the relation between the layer(s) in which the compounds are incorporated and a silver halide emulsion, and the kind of an antifoggant.
• the addition amount of the compound of formula (la) for use in the present invention is preferably from 5 mg/m 2 to 500 mg;m 2 , and 10 mg/m 2 to 250 mg / m 2 is particularly preferred.
• the addition amount of the compound of formula (Ib) is preferably from 1 mg/m 2 to 250 mg / m 2 , and 3 mg/m 2 to 150 mg/m 2 is particularly preferred.
• the addition amount of the compound of formula (IX) is preferably from 1 mg/m 2 to 300 mg/m 2 , and 2 mg/m 2 to 200 mg/m 2 is particularly preferred.
• the compound of formula (IX) wherein R 2' contains therein a group enhancing the adsorption onto the surface of silver halide grains is preferably added in an amount of from 2 mg/m 2 to 100 mg / m 2 .
• the photographic emulsion for use in the present invention may contain silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, silver iodide, or silver chloride, but it is preferred that the silver halide contains at least 50 mol% silver chloride.
• the silver halide grains in the photographic emulsion may have a regular crystal form such as cubic, octahedral, dodecahedral, tetradecahedral, etc.; an irregular crystal form such as sphere, tabular, etc.; or a composite of these crystal forms.
• the silver halide grains may be composed of a mixture of grains having various crystal forms.
• the silver halide grains for use in the present invention may have different phase between the inside and the surface layer thereof or may be composed of a uniform phase throughout the whole grain.
• a cadmium salt a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, rhodium salt or a complex salt thereof, iron salt or a complex salt thereof, etc.
• a cadmium salt a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, rhodium salt or a complex salt thereof, iron salt or a complex salt thereof, etc.
• a silver halide solvent e.g., ammonia, potassium rhodanate, and thioethers and thione compounds as described in U.S. Patent 3,271,157, JP-A-51-12360, JP-A-53-82408, JP-A-53-144319, JP-A-54-100717, and JP-A-54-155828
• a silver halide solvent e.g., ammonia, potassium rhodanate, and thioethers and thione compounds as described in U.S. Patent 3,271,157, JP-A-51-12360, JP-A-53-82408, JP-A-53-144319, JP-A-54-100717, and JP-A-54-155828
• the silver halide emulsion for use in the present invention may or may not be chemically sensitized.
• Chemical sensitization for use in the present invention include a sulfur sensitization method using active gelatin or a sulfur-containing compound capable of reacting with silver (e.g., thiosulfates, thioureas, mercapto compounds, and rhodanines); a reduction sensitizing method using a reducing material e.g., stannous salt, amines, hydrazine derivatives, formamidinesulfinic acid, silane compounds, etc.); a noble metal sensitization method using a metal compound (e.g., gold complex salts and complex salts of noble metals belonging to group VIII of the Periodic Table, such as Pt, Ir, Pd, etc.); or a combination thereof.
• a sulfur sensitization method using active gelatin or a sulfur-containing compound capable of reacting with silver e.g., thiosulfates, thioure
• the silver halide emulsions for use in this invention can contain various compounds for preventing the formation of fog during the storage and/or photographic processing of the light-sensitive material or for stabilizing photographic performance.
• antifoggants or stabilizers include azoles (e.g., benzothiazoliums, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (in particular, nitro- or halogen- substituted benzimidazoles)); heterocyclic mercapto compounds (e.g., mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (in particular, 1-phenyl-5-mercaptotetrazole), and mercaptopyrimidines), the aforesaid heterocyclic mercapto compounds having a water-solubilizing group such as a carboxy group and a sulfon group
• ox- azolinethione ox- azolinethione
• azaindenes e.g., tetraazaindenes (in particular, 4-hydroxy-substituted (1.3,3a.7)-tetraazaindenes
• benzenethiosulfonic acids e.g., benzenethiosulfonic acids, and benzenesulfinic acid.
• the photographic emulsion for use in the present invention may be spectrally sensitized to relatively a long wavelength of blue light, green light, red light, or infrared light using sensitizing dyes.
• sensitizing dyes include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, styryl dyes, hemicyanine dyes, oxonol dyes, hemioxonol dyes, etc.
• the photographic light-sensitive material being processed in the present invention may contain water-soluble dyes in the hydrophilic colloid layer(s) as filter dyes or for irradiation inhibition, etc.
• dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes.
• oxonol dyes, hemioxanol dyes, and merocyanine dyes are particularly useful.
• the photographic light-sensitive material of the present invention may further contain in the photographic emulsion layer(s) and other hydrophilic colloid layer(s) an inorganic or organic hardening agent.
• an inorganic or organic hardening agent e.g., active vinyl compounds (e.g., 1,3,5-triacryloyl-hexahydro-s-triazine and 1,3- vinylsulfonyl-2-propanol) and active halogen compounds (e.g., 2,4-dichloro-6-hydroxy-s-triazine) can be used singly or as a combination thereof.
• the photographic light-sensitive material of the present invention may further contain in the photographic emulsion layer(s) or other hydrophilic colloid layer(s) various surface active agents.
• nonionic surface active agents such as saponin (steroid series), alkylene oxide derivatives (e.g., polyethylene glycol, polyethylene glycolipolypropylene glycol condensates, polyethylene glycol alkyl ethers, polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkylamines, polyalkylene glycol alkylamides, and polyethylene oxide addition products of silicone), glycidol derivatives (e.g., alkenyl succinic acid polyglyceride and alkylphenol polyglyceride), aliphatic acid esters of polyhydric alcohols, alkyl esters of saccharide, etc.; anionic surface active agents containing an acid group (e.g., a carboxy group, a sulfo group, a phospho group, a sulfuric acid ester group, and a phosphoric acid ester
• an acid group e.g.,
• the photographic emulsion layer(s) of the photographic light-sensitive material of the present invention may further contain polyalkylene oxide or the derivatives thereof such as the ethers, esters, amines, etc., thereof, thioether compounds, thiomorpholines, quaternary ammonium salt compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidone derivatives, etc., for increasing sensitivity, contrast, and/or accelerating development.
• polyalkylene oxide or the derivatives thereof such as the ethers, esters, amines, etc., thereof, thioether compounds, thiomorpholines, quaternary ammonium salt compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidone derivatives, etc.
• gelatin is advantageously used, but other hydrophilic colloids can also be used.
• hydrophilic high molecular materials such as polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polyacrylamide, dextran, etc. may be used.
• a stable developer can be used without use of either a conventional infectious developer or a high alkaline developer of about pH 13 as described in U.S. Patent 2,419.975.
• super high contrast negative images are obtained by processing the light-sensitive material of the present invention with a developer containing a sulfite ion at a concentration of at least 0.15 mol/liter and having pH of from 9.6 to 11.0, and particularly from 10.0 to 11.0.
• the developing agent which can be used in the process of the present invention and, for example, dihydroxybenzenes (e.g., hydroquinone), 3-pyrazolidones (e.g., 1-phenyl-3-pyrazolidone, 4,4-dimethyl-1-phenyl-3-pyrazolidone), and aminophenols (e.g., N-methyl-p-aminophenol) can be used singly or in combination thereof.
• dihydroxybenzenes e.g., hydroquinone
• 3-pyrazolidones e.g., 1-phenyl-3-pyrazolidone, 4,4-dimethyl-1-phenyl-3-pyrazolidone
• aminophenols e.g., N-methyl-p-aminophenol
• the silver halide light-sensitive material of the present invention is preferably processed by a developer containing a dihydroxybenzene as the primary developing agent and a 3-pyrazolidone or an aminophenol as an auxiliary developing agent.
• the developer contain the dihydroxybenzene in the range of from 0.05 to 0.5 mol;liter and the 3-pyrazolidone or aminophenol in the range of less than 0.06 mol/liter.
• the developer for use in the present invention may further contain pH buffers such as sulfites, carbonates, borates, and phosphates of an alkali metal or a development inhibitors or antifoggants such as bromides, iodides and organic antifoggants (nitroindazoles or benzotriazoles are particularly preferred).
• the developer may contain a water softener, a resolution aid, a toning agent, a development accelerator, a surface active agent (a polyalkylene oxide is particularly preferred), a defoaming agent, a hardening agent, and or a silver stain inhibitor of films (e.g., 2-mercaptobenzimidazole sulfonic acids).
• the silver halide light-sensitive material is fixed in the present invention.
• Ordinary fixing compositions can be employed including thiosulfates, thiocyanates, and organic sulfur compounds which are known to have an effect as fixing agent.
• the fix solution may contain a water-soluble aluminum salt as a hardening agent.
• the processing temperature in the process of the present invention is typically from 18° C to 50 C.
• An automatic processor is preferably used for the photographic processing of the present invention. Even when the total processing time is in the range of from 90 seconds to 120 seconds., negative photographic characteristics of super high contrast are obtained.
• the developer for use in the present invention may contain the compound disclosed in JP-A-56-24347 as a silver stain inhibitor. Furthermore, the developer may contain the compound disclosed in JP-A-61-267759 as a resolution aid. Moreover, the developer may further contain the compound disclosed in JP-A-60-93433 or boron compounds disclosed in JP-A-62-186259.
• a silver chloroiodobromide emulsion (containing 0.1 mol% silver iodide and 30 mol% silver bromide) was prepared using a double jet method as shown below.
• (NH 4 ) 3 RhCl 6 was added to the aqueous halide solution (containing KBr, NaCt and KI)as a rhodium salt at a concentration of 5x10 -6 mol/mol-Ag.
• K 3 IrCl 6 was also added to the aqueous halide solution as an iridium salt at a concentration of 4x10 -7 mol/mol-Ag.
• aqueous halide solution thus prepared and an aqueous silver nitrate solution were added to an aqueous gelatin solution and mixed for 60 minutes at 45°C to provide a mono-dispersed cubic grain size halide having a mean grain size of 0.25 ⁇ m.
• 1x10 -5 mol/mol-Ag of sodium thiosulfate and 1x10 -5 mol/mol-Ag of potassium chloroaurate were added to the emulsion for gold sensitization.
• each of IX-9, IX-31, IX-20, IX-32, IX-34, and IX-35 as the hydrazine compound shown by formula (IX) and each of la-15 and Ib-7 as a nucleation accelerator as shown in Table 1 below to provide the silver halide emulsion.
• a coating composition for a protective layer was composed of an aqueous gelatin solution containing gelatin, sodium dodecylbenzenesulfonate, colloidal silica, a dispersion of polyethyl acrylate, polymethyl methacrylate (matting agents), and sodium polystyrenesulfonate (tackifier).
• the aforesaid emulsion and the coating composition for the protective layer were simultaneously coated on a transparent plastic film support at a gelatin coverage of 1.6 gim 2 for the protective layer and a silver coverage of 3.6 g/m 2 for the emulsion layer.
• Each sample thus prepared was exposed to tungsten light of 3200 K through a sensitometric optical wedge for 5 seconds, developed by developer (A) or (D) having the composition shown below for 30 seconds at 38 C, fixed, washed, and dried.
• An automatic processor FG-660F, made by Fuji Photo Film Co., Ltd. was used for the development processing.
• Developer (D) was prepared by adding acetic acid to developer (A) reducing the pH to 10.4.
• Developers (B), (C), (D), (E), (F), and (G) were prepared having the same composition as the developer in Example 1 except that the pH value was adjusted as shown in Table 2.
• Light-sensitive film prepared as in Sample No. 9 of Example 1 was processed using the developer of Example 1, as adjusted for pH, and the G value was then measured. The results are shown in Table 2.
• the light-sensitive film was processed using the one week old developer and the G value was measured. The results are also shown in Table 2.

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• 1989
  • 1989-01-10 DE DE68926687T patent/DE68926687T2/de not_active Expired - Fee Related
  • 1989-01-10 EP EP89100317A patent/EP0324426B1/fr not_active Expired - Lifetime

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