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
  • G03C1/42—Developers or their precursors
• • 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

Definitions

• high-contrast photographic images are used for the formation of charactor images or color separation halftone dot images in the photomechanical process or for the formation of finely detailed line drawing images in the super-high resolution photomechanical process. Accordingly, certain silver halide photographic materials for use in such processes are known to be capable of forming very high-contrast photographic images.
• a conventional image-forming method in which a light-sensitive material comprised of a silver chlorobromide emulsion whose silver halide grains have an average grain size of, for example, 0.2 um, a narrow grain size distribution and uniform configuration and whose silver chloride content is as high as at least 50 mole% is processed in an alkaline hydroquinone developer solution having a low sulfite ion concentration to thereby obtain high-contrast, high-sharpness and high-resolution images such as, e.g., halftone dot or fine line drawing images.
• Silver halide light-sensitive materials of such the kind are known as lith-type light-sensitive materials.
• the photomechanical process includes a process for converting a continuous-tone original image into a halftone dot image, i.e., the process for converting changes in the density of the continuous tone of an original into an assemblage of dots having areas proportional to the respective densities.
• the above-mentioned lith-type light-sensitive material is used, exposed through a crossline screen or contact screen to an original image, and then developed, whereby a halftone dot image is formed.
• a silver halide light-sensitive photographic material having a fine-grained silver halide emulsion comprising silver halide grains uniform in the grain size as well as in the grain configuration is used, but even when a light-sensitive material of this kind is used, if processed in a developer solution for general black and-white developing use, the obtained results will be inferior in the halftone dot image formation to those obtained when processed in a lith-type developer solution. Therefore, the light-sensitive material should be processed in a lith-type developer solution of a single hydroquinone developing agent and an extremely low sulfite ion concentration.
• the lith-type developer solution since its preservability is very poor due to its proneness to undergo autoxidation, essentially needs a control method to keep its developing quality constant even when used continuously over a long period. Every effort has hitherto been made to improve the preservability of this developer solution.
• a replenishing method which, in order to retain the lith-type developer solution's preservability, separately uses both a replenisher to make up for the deterioration of the solution's activity due to development (processing fatigue replenishment) and a replenisher to make up for the exhaustion of the solution due to its autoxidation in time (spontaneous fatigue replenishment), the so-called two-liquid separately replenishing method is generally widely employed in automatic processors for photomechanical process use.
• the above method however, has the disadvantage that it requires control of replenishing balance of the two liquids, thus complicating the processor as well as its operation.
• the lith-type developer solution is unable to quickly provide processed images because it takes time (introduction period) until when an image begins to appear in its developing process.
• any of these methods requires the use of a fairly high pH-having developer solution in order to give a high-contrast image, so that they come into question in respect of the developer solution's stability if they are to be used as the technique to provide high-sensitivity images rapidly.
• this developer solution has another disadvantage that its pH is so high as to tend to fog the light-sensitive material in processing, motivating the incorporation of various organic antifoggants in a high concentration into the solution, thus resulting in the sacrifice of the sensitivity.
• a method for forming an image comprising a step of development of a silver halide photographic light-sensitive material having a silver halide emulsion layer in a developer, wherein said silver halide emulsion layer contains a compound selected from the group consisting of 3-pyrazolidone-type compounds, dihydroxybenzene-type compounds or trihydroxybenzene-type compounds, and the developer contains a compound selected from the group consisting of dihydroxybenzene-type compounds and trihydroxybenzene-type compounds, a sulfite and amino compounds; said development being performed in the presence of a compound selected from the group consisting of compounds represented by the following Formulas 1, 2 and 3: wherein R, and R 2 each represents an aryl group or a heterocyclic group, R represents a divalent organic group, n is an integer of zero to 6, and m is an integer of zero to 1, provided that when n is 2 to 6, the Rs are the same as or different from each other, wherein R 21 is an alipha
• R 1 and R 2 each represents an aryl group or a heterocyclic group, which each may have a substituent;
• R is a divalent organic group, n is an integer of zero to 6; and
• m is an integer of zero or 1.
• the aryl group represented by the R 1 or R 2 is a phenyl naphthyl or the like group, and the heterocyclic group is a pyridyl, benzothiazolyl, quinolyl, thienyl or the like group, but the R 1 or R 2 is preferably the aryl group.
• the aryl group or heterocyclic group represented by the R 1 or R 2 include those having one of various substituents, examples of which include a halogen atom such as chlorine, bromine, etc.; an alkyl group such as methyl, ethyl, dodecyl, etc.; an alkoxy group such as methoxy, ethoxy, isopropoxy, butoxy, octyloxy, dodecyloxy, etc., an acylamino group such as acetylamino, pivalylamino, benzoylamino, tetradecanoylamino, a-(2,4-di-t-amylphenoxy)butylamino, etc.; a sulfonylamino group such as methanesulfonylamino, butanesulfonylamino, dodecanesulfonylamino, benzenesulfonylamino, etc.; an ure
• the divalent organic group represented by the R is, for example, an alkylene group such as methylene, ethylene, trimethylene, tetramethylene, etc.; an arylene group such as phenylene naphthylene etc.; an aralkylene group; or the like, but the alkylene group may contain in its linkage an oxygen atom, sulfur atom, selenium atom, carbonyl group, R - N - group (wherein R 3 represents a hydrogen atom, alkyl group or aryl group), sulfonyl group, or the like.
• the group represented by the R includes one having one of various substituents, examples of which include a -CONHNHR4 group (wherein R 4 . is as defined in the foregoing R 1 and R 2 ), alkyl group, alkoxy group, halogen atom, hydroxy group, carboxy group, acyl group, aryl group, and the like.
• R is the alkylene group.
• the aliphatic group represented by R 21 is preferably one having 6 or more carbon atoms, and particularly a straight-chain, branched-chain or cyclic alkyl group having from 8 to 50 carbon atoms, wherein the branched-chain alkyl group is allowed to be so cyclized as to form an unsaturated heterocyclic ring containing therein one or more hetero atoms.
• this alkyl group includes one having such as an aryl, alkoxy or sulfoxy group.
• the aromatic group represented by the R 21 is preferably a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group, wherein the unsaturated heterocyclic group may be condensed with a monocyclic or bicyclic aryl group to form a heteroaryl group.
• Examples of the ring of such cyclic groups include benzene ring, naphthylene ring, pyridine ring, pyrimidine ring, imidazole ring, pyrazole ring, quinoline ring, isoquinoline ring, benzimidazole ring, thiazole ring, benzothiazole ring, and the like. Out of these, those groups containing the benzene ring are preferred.
• R 21 is an aryl group.
• the aryl group or unsaturated heterocyclic group repre sented by the R 21 includes one having a substituent, typical examples of which include straight-chain, branched-chain or cyclic alkyl groups such as those monocyclic or bicyclic ones of which the alkyl portion's number of carbon atoms is from 1 to 20; alkoxy groups having preferably from 1 to 20 carbon atoms; substituted amino group, preferably amino groups substituted by an alkyl group having from 1 to 20 carbon atoms; acylamino groups having preferably from 2 to 30 carbon atoms; sulfonamido groups having preferably from 1 to 30 carbon atoms; ureido groups having preferably from 1 to 30 carbon atoms; and the like.
• the substitutable alkoxy group is one having from 1 to 20 carbon atoms, and may be substituted by a halogen atom, an aryl group or the like.
• the substituted aryloxy group or heterocycloxy group is preferably monocyclic, and substituents to these groups include a halogen atom, alkyl group, alkoxy group, cyano group and the like.
• amino group it is represented by wherein A, and A 2 each represents a substitutable alkyl group or alkoxy group or may be a cyclic group of a structure containing -0-, -S- or -N- group linkage, provided that the R 22 is no hydrazino group.
• the R 21 or R 22 of Formula 2 may be one into which is incorporated a ballasting group that is usually used in immobile photographic additives such as couplers.
• the ballasting group is a relatively photographically inactive group having 8 or more carbon atoms, which may be selected from among, for example, alkyl groups, alkoxy groups, phenyl group, alkylphenyl groups, phenoxy group, alkylphenoxy groups, and the like.
• the R 21 or R 22 of Formula 2 may be one into which is incorporated a group that strengthens the adsorption to the silver halide grain surface.
• adsorption group include those groups as described in U.S. Patent No. 4,355,105 such as thiourea group, heterocyclic thioamido group, mercapto heterocyclic group, triazole group, and the like.
• R 23 and R 24 each represents a hydrogen atom, a substitutable alkyl group such as methyl, ethyl, butyl, dodecyl 2-hydroxypropyl, 2-cyanoethyl, 2-chloroethyl or the like, substitutable phenyl group, naphthyl group, cyclohexyl group, pyridyl group, pyrrolidyl group, such as phenyl, p-methyl phenyl, naphthyl, a-hydroxynaphthyl, cyclohexyl, p-methylcyclohexyl, pyrdiyl, 4-propyl-2-pyridyl, pyrrolidyl, 4-methyl-2-pyrrolidyl, etc.; R 25 is a hydrogen atom or a substitutable benzyl, alkoxy or alkyl group, such as benzyl
• Ar is an aryl group containing at least one nondiffusible group or silver halide adsorption accelerating group.
• a ballasting group that is usually used in immobile photographic additives such as couplers is preferred.
• the ballasting group is a relatively photographically inactive group having 8 or more carbon atoms, which may be selected from among, for example, alkyl groups, alkoxy groups, phenyl group, alkylphenyl groups, phenoxy group, alkylphenoxy groups, and the like.
• silver halide adsorption accelerating group examples include those groups as described in U.S. Patent No. 4,385,108, such as thioureido group, thiourethano group, heterocyclic thioamido group, mercapto heterocyclic group, triazolyl group, and the like.
• R31 represents a substituted alkyl group.
• the alkyl group is a straight-chain, branched-chain or cyclic alkyl group, such as methyl, ethyl, propyl, butyl, isopropyl, pentyl, cyclohexyl or the like.
• Examples of the substituent to be introduced to these alkyl groups include alkoxy groups such as methoxy, ethoxy, etc.; aryloxy groups such as phenoxy, p-chlorophenoxy, etc.; heterocycloxy groups such as pyridyfoxy; mercapto group, alkylthio groups such as methylthio, ethylthio, etc.; arylthio groups such as phenylthio, p-chlorophenylthio, etc.; heterocyclic thio groups such as pyridylthio, pyrimidylthio, thiadiazolyl- thio, etc.; alkylsulfonyl groups such as methanesulfonyl, butanesulfonyl, etc.; arylsulfonyl groups such as benzene sulfonyl; heterocyclic sulfonyl groups such as pyridylsulfonyl
• cyano group chlorine; bromine; alkoxycarbonyl groups such as ethoxycarbonyl, methoxycarbonyl, etc.; aryloxycarbonyl groups such as phenoxycarbonyl; carboxy group, carbamoyl group; alkylcarbamoyl groups such as N-methylcarbamoyl, N,N-dimethylcarbamoyl, etc.; arylcarbamoyl groups such as N-phenylcarbamoyl: amino group; alkylamino groups such as methylamino N,N-dimethylamino, etc.; arylamino groups such as phenylamino, naphthylamino, etc.; acylamino groups such as acetylamino, benzoylamino, etc.; alkoxycarbonylamino groups such as ethoxycarbonylamino; aryloxycarbonylamino groups such as phenoxycarbonylamino; acyl
• the hydrogen atom of the hydrazine may be substituted by a sulfonyl group such as methanesulfonyl, toluenesulfonyl, etc.; an acyl group such as acetyl, trifluoroacetyl, etc.; an oxalyl group such as ethoxalyl, or the like.
• a sulfonyl group such as methanesulfonyl, toluenesulfonyl, etc.
• an acyl group such as acetyl, trifluoroacetyl, etc.
• an oxalyl group such as ethoxalyl, or the like.
• reaction liquid was poured into 1 liter of water, and the separated oily phase was decanted and dissolved into 300 ml of chloroform, and then washed by dilute alkaline water.
• the separated chloroform phase was dehydrated by adding MgS0 4 thereto and then filtered.
• reaction liquid after being stirred for 10 minutes at room temperature, was poured into 500 ml of iced water, then neutralized by sodium carbonate, and then extracted by chloroform:
• the chloroform phase was washed by water, dehydrated by MgSO 4 , then filtered, and then concentrated, whereby 9.3 g of crude product were obtained.
• the hydrazide compound having Formula 1, 2 or 3 should be contained in the light-sensitive material and/or a developer solution.
• the compound should be incorporated into a light-sensitive silver halide emulsion layer containing a 3-pyrazolidone compound and a di- or trihydroxybenzene-type compound and/or at least one of other layers on the support from which the compound can be diffused to move into the emulsion layer at least by the time of development.
• the amount of the hydrazide compound is preferably from 1 ⁇ 10 -6 to 1 ⁇ 10 -1 mole, and more preferably from 1 ⁇ 10 -4 to 1 ⁇ 10 -2 mole per mole of silver halide. Its suitable amount may be discretionarily determined, taking into account the composition, grain sizes and degree of chemical ripening of the silver halide to be used, the amount of a hydrophilic colloid as the binder of layers, and its balance with additives such as stabilizer, restrainer, accelerating agent, and the like.
• its adding amount is from 10- 5 to 10- 2 mole, and preferably from 10- 4 to 10- 3 mole per liter of the developer solution, and its suitable amount may be determined, taking into account its balance with the amino compound to be present together, pH, antifoggant, and the like.
• the 3-pyrazolidone compound to be contained in the light-sensitive material for use in the method of this invention is a compound having the following Formula: wherein R' is a substitutable aryl group, R 2 , R 3 and R 4 each represents a hydrogen atom or a substitutable alkyl group.
• R' is a substitutable aryl group
• R 2 , R 3 and R 4 each represents a hydrogen atom or a substitutable alkyl group.
• the substituent to the aryl group represented by the R' is, for example, a methyl, chloro, amino, methylamino, acetylamino, methoxy or methylsulfonamidoethyl group.
• the aryl group represented by the R' is, for example, a phenyl, p-aminophenyl, p-chlorophenyl, p-acetamidophenyl, p-methoxyphenyl or the like group.
• the alkyl group represented by the R 2 , R 3 or R 4 may be in any of the straight-chain, branched-chain or cyclic form, and is preferably one having from 1 to 8 carbon atoms and being allowed to have a substituent such as, e.g., a hydroxy, carb oxy, sulfo or the like group.
• the alkyl group is such as, for example, a methyl, hydroxymethyl, ethyl or propyl group.
• the position of the compound inside the light-sensitive material is to be in the light-sensitive silver halide emulsion layer, but may also be in non-emulsion layers such as the protective layer, intermediate layer, subbing layer, backing layer, etc.
• Incorporation of the compound should be made generally in the form of a solution of it dissolved in an organic solvent. Its adding amount is from 10 -6 to 10 -1 mole per mole of silver halide, but when it is in the range of from 10- 4 to 10- 2 mole, the best results can be obtained.
• the di- or trihydroxybenzene compound to be contained in the light-sensitive material and developer solution for use in the image forming method of this invention is a compound having the formula: wherein R", R 12 and R 13 each represents a hydrogen atom, a halogen atom, an alkyl group or a substituted alkyl group, an aryl group or a substituted aryl group, a heterocyclic group or a substituted heterocyclic group, a -0-R' 4 group, or a -S-R' 4 group, wherein R 14 is a hydrogen atom, an alkyl group or a substituted alkyl group, an aryl group or a substituted aryl group, or a heterocyclic group or a substituted heterocyclic group; and n is an integer of zero or 1.
• the position of the compound inside the light-sensitive material of this invention is to be in the light-sensitive silver halide emulsion layer, but may also be in non-emulsion layers such as the protective layer, intermediate layer, subbing layer, backing layer, etc.
• Incorporation of the compound should be made generally in the form of a solution of it dissolved in water or an organic solvent including alcohols such as methanol, ethanol, etc.; glycols such as diethylene glycol, triethylene glycol, etc.; ketones such as acetone; or the like. Its adding amount is from 0.001 to 0.10 mole per mole of silver halide, and preferably from 0.005 to 0.03 mole.
• hydroquinone widely used in general photographic processing, is most preferred, and its adding amount is normally from 0.05 to 0.5 mole per liter.
• the sulfite to be contained in the developer solution for use in the method of this invention may be one that is usually used in developer solutions for use in developing ordinary silver halide photographic light-sensitive materials, and examples of it include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, addition compound of formaldehyde with sodium bisulfite, and the like.
• the sulfite's concentration need only be such a concentration as to protect the developer solution from air oxidation to thereby enable to obtain a sufficient sulfite ion concentration for providing stable photographic characteristics, and thus its adding amount needs to be not less than 0.05 mole per liter, and preferably more than 0.15 mole per liter.
• the amino compound to be contained in the developer solution for use in the method of this invention is used for the purpose of accelerating the increase in image contrast; particularly, of enhancing its effect even on a relatively low pH level of the developer solution.
• Those useful amino compounds for this invention include inorganic amines and organic amines.
• the organic amine can be an aliphatic amines aromatic amine, cyclic amine, aliphatic-aromatic mixture amine, or heterocyclic amine. Primary amines, secondary amines, tertiary amines and quaternary ammonium compounds have been all found out to be effective.
• Alkanolamines particularly suitable for object of this invention have the formula: wherein R 21 is a hydroxyalkyl group having 2 to carbon atoms; R 22 and 23 each represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a hydroxyalkyl group having 2 to 10 carbon atoms, a benzyl group or a group having the formula: wherein n is an integer of 1 to 10, and X and Y each is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a hydroxyalkyl group having 2 to 1o carbon atoms.
• alkylamines particularly those having the formula: wherein R 24 is an alkyl group having 1 to 10 carbon atoms; and R 25 and R 26 each represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
• the adding amount of the amino compound to be used in this invention is in the range of from 0.01 to 1.0 mole per liter, and preferably from 0.01 to 0.04 mole per liter.
• the developer solution to be used in this invention is desirable to contain 5- or 6-nitroindazole.
• the compound is considerably effective in preventing a light-sensitive material from being fogged and keeping its sensitivity and contrast high. Its suitable adding amount is in the range of from 0.0001 to 0.1 mole per liter of the developer solution.
• the developer solution for use in the method of this invention may contain a 3-pyrazolidone compound or o- or p-aminophenol compound as a developing agent in addition to the dihydroxybenzene-type compound.
• the suitable pH range of the developer solution is from 10 to 12.
• an alkali metal hydroxide or carbonate may be added as an alkali agent to the developer solution.
• an inorganic antifoggant such as potassium bromide and an organic antifoggant including a triazole compound such as 5-methylbenzotriazole, 5-chlorobenzotriazole; a mercapto compound such as 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole; or the like, may be used.
• the developer solution for use in the method of this invention may contain arbitrary additives according to purposes in addition to the foregoing components.
• additives include solvents, buffers, sequestering agents, development accelerators, viscosity increasing agents, emulsion layer's swelling restraining agents, and the like.
• the processing in the method of this invention may take place under various conditions: developing temperature is preferably not more than 50 C, and more preferably around 40 C, and developing time is generally within three minutes; particularly, in many cases, developing within two minutes produces good results.
• other processes such as, e.g., washing, stopping, stabilizing, fixing and at need additional processes such as prehardening, neutralizing, etc., may be arbitrarily employed and may also be distretionarily omitted.
• these processings may be made in manual manner such as tray development, frame development, or in mechanical way such as roller development, hanger development, or the like.
• silver halide emulsion of the light-sensitive material to be used in this invention various silver halides may be used, such as silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, or the like.
• This invention exhibits its effect significantly when an emulsion of a silver halide composition containing not less than 50 mole% silver bromide is used, and is particularly effective to a high-speed light-sensitive material having less silver iodide (not more than 5 mole% Agl).
• the silver halide suitably usable in the silver halide emulsion layer in this invention is silver chlorobromide or silver chloroiodobromide containing not less than 50 mole% silver bromide. If the silver bromide content is less than 50 mole%, a fog including pepper fog tends to appear on the processed film.
• the silver halide to be contained in the silver halide emulsion layer of the light-sensitive material for use in this invention is desirable to be of silver halide grains whose average grain size is from 0.1 to 1.0 ⁇ m, particularly preferably from 0.1 to 0.7 ⁇ m, and which contain grains having sizes 0.7 to 1.3 times the average grain size accounting for at least 75%, particularly preferably more than 80% of the whole silver halide grains.
• the crystal habit of the silver halide grain may be either cubic or octahedral, and may also be of the tablet type as disclosed in Japanese Patent O.P.I. Publication No. 10852/1983.
• the method of preparing silver halide grains of the silver halide emulsion layer in this invention may be the single-jet method according to the orderly mixing method, inversely mixing method, etc., or the double- jet method according to the simultaneously mixing method, and of these the particularly preferred is the simultaneously mixing method.
• the preparation may be made according to the ammoniacal process, neutral process, acidic process, or the modified ammoniacal process as disclosed in Japanese Patent Examined Publication No. 3232/1983, of which the particularly preferred is the acidic process or neutral process.
• silver halide grains may contain thereinside metal atoms such as iridium, rhodium, osmium, bismuth, cobalt, nickel, ruthenium, iron, copper, zinc, lead, cadmium, etc.
• metal content of silver halide grains is desirable to be 10- 8 to 10- 5 mole per mole of the silver halide.
• the silver halide grain is desirable to be of the surface latent image type.
• the silver halide photographic emulsion of the silver halide emulsion layer according to this invention may be subjected to chemical sensitization.
• the chemical sensitization includes sulfur sensitization, reduction sensitization and noble-metal sensitization.
• the chemical sensitization is desirable to be made by the sulfur sensitization alone.
• the sulfur sensitizer the sulfur compound contained in gelatin and various sulfur compounds such as, e.g., thiosulfates, thioureas, thiazoles, rhodanines and the like may be used; more particularly, those sulfur sensitizers as described in U.S. Patent Nos. 1,574,944, 2,410,689, 2,728,668, and Japanese Patent Examined Publication No. 11892/2984 may be used.
• the silver halide light-sensitive photographic material of this invention is desirable to further contain those compounds having the following Formulas 4, 5, 6 or 7 from the antifogging point of view.
• A is a phosphorus atom or a nitrogen atom
• R 4-1 , R 42 , R 43 , and Rt4 each represents a substituted or unsubstituted alkyl, aryl or aralkyl group
• X- is an acid anion.
• Y and Z each represents a nitrogen atom or a carbon atom, provided that when either one of the Y and Z is a nitrogen atom, the other is a carbon atom
• R 51 is a hydrogen atom, a lower alkyl group, a halogen atom or a nitro group.
• R 61 R 62 and R 63 each represents a hydrogen atom, an amino group, a hydroxy group, a mercapto group, an alkyl group or an aryl group.
• L 1 through L4 each represents a divalent hydrocarbon group
• Y represents a hydrogen atom, a divalent group or a linkage, or an amino group
• Z is a heterocyclic group
• G is a sulfonic group, a carboxyl group or a phosphonic acid group
• R 71 and R 72 each represents a hydrogen atom, an alkyl group or an aryl group
• k, I, m and n each is an
• the alkyl group which is allowed to have a substituent, represented by the R 41 , R 42 , R 43 or R 44 is preferably a lower alkyl group having from 1 to 8 carbon atoms such as methyl, ethyl, isopropyl, n-butyl or octyl group, and the substituent to the alkyl group is, for example, a hydroxy, sulfo, carboxy or amino group or a halogen atom.
• the aryl group which may have a substituent, represented by the R 41 , R 42 , R 43 or R 44 is a phenyl or naphthyl group, and preferably the phenyl group.
• the substituent to the aryl group is an alkyl group, preferably a lower alkyl group having 1 to 8 carbon atoms; an alkoxycarbonyl group; an alkylsulfonyl group, an alkylcarbonyl group, the alkyl portion of which groups has 1 to 8 carbon atoms; a nitro group, a cyano group, a halogen atom, a -N(C 2 H 5 )2HCI- group, or the like.
• the aralkyl group which may have a substituent represented by the R 41 , R 42 , R 43 or R 44 is, for example, a benzoyl, phenyl or the like group, and preferably the benzoyl group.
• the substituent to the aralkyl group includes, for example, the same groups as those to the above aryl group.
• the substituent to the electron attractive group owned by the aryl or aralkyl group represented by the R 41 , R 42 , R 43 or R 44 is typified by a halogen atom or a nitro, cyano, carbonyl, carboxyl, sulfonyl or quaternary amino group.
• the anion represented by the X- is a chloride ion, bromide ion, iodide ion, cyanide ion, hypochlorite ion, p-toluene-sulfonate ion, benzene-sulfonate ion, hydroxide ion, or the like.
• the compound having Formula 4 may be easily synthesized in accordance with the method described in Japanese Patent Examined Publication No. 40665/1975.
• Incorporation of the compound having Formula 4 into the component of a silver halide light-sensitive photographic material should be made in the manner that the compound is dissolved in water or in an organic solvent arbitrarily miscible with water, such as methanol or ethanol, and the solution is then incorporated into the component.
• the adding amount of the compound although it depends on the types of the silver halide, component, compound, etc. to be used, is generally from 10- 7 to 10- 3 mole per mole of silver halide, and more preferably from 10- 6 to 10- 4 mole.
• the lower alkyl group represented by the R 51 may be a straight-chain or branched-chain alkyl group having 1 to 8 carbon atoms, such as methyl, ethyl, isopropyl or butyl group.
• any of these compounds having Formula may be used in the adding amount range of from 1 ⁇ 10 -5 to 1 ⁇ 10 -1 mole per mole of silver halide, and more preferably from 1 ⁇ 10 -4 to 1 ⁇ 10 -2 mole. Incorporation of the compound may be performed in accordance with that of the compound having Formula 1.
• the alkyl group represented by the R 61 , R 62 or R 63 may be either straight-chain or branched-chain, preferably having from 1 to 16 carbon atoms, such as methyl, ethyl or a long-chain alkyl group like dodecyl group.
• the aryl group represented by the R 61 , R 62 or R 63 is a phenyl or naphthyl group.
• any of these compounds having Formula 6 is used in the adding amount range of from 1 ⁇ 10 -5 to 1 ⁇ 10 -1 mole per mole of silver halide, and more preferably from 1x10- 4 to 1 ⁇ 10 -1 mole. Incorporation of the compound may be performed in accordance with that of Formula 1.
• the divalent hydrocarbon group represented by the L 1 to L 4 is, for example, an alkylene, arylene or aralkylene group.
• the alkylene group is preferably a straight-chain or cyclic one having from 1 to 15 carbon atoms, such as, e.g., a methylene, ethylene, propylene, pentamethylene, dodecamethylene, 1,6-cyclohexylene or the like group.
• the arylene group represented by the L 1 or L 2 is, for example, a 1,4-phenylene, 1,3-phenylene, 1,4-naphthylene, 1,4-anthraquinolylene or the like group.
• the aralkylene group is, for example, a benzylene, phenethylene or the like group.
• the amidino group represented by the Y includes one having a substituent.
• the substituent is, for example, an a]ky] group such as methyl, ethyl, benzyl etc., an aryl group such as a phenyl, p-tolyl, naphthyl, etc., or a heterocyclic group such as 2-thiazolyl, 2-pyridyl, 4 imidazolyl, etc.
• the heterocyclic group represented by the Z is preferably a 5- to 7-member cyclic group, which includes those condensed with a benzene ring, naphthalene ring, 5- or 6-member heterocyclic ring or 5- or 6-member aliphatic ring; e.g., such heterocyclic rings as furan, thiophene, benzo[b]thiophene, imidazole, benzimidazole, pyrrole, s-triazine pyrimidine, quinoline, indole, benzoxazole, benzothiazole, and the like.
• the alkyl group represented by the R 71 or R 72 is. e.g., a methyl, ethyl, propyl or the like group, and the aryl group is, e.g., a phenyl or naphthyl group.
• the divalent hydrocarbon group represented by the L 1 to L 4 , the alkyl and aryl groups each represented by the R 71 or R 72 , and the heterocyclic group represented by the Z include those each having a substituent.
• substituents include, e.g., alkyl groups such as methyl, ethyl, sec-propyl, etc.; alkoxy groups such as methoxy, ethoxy, etc.; amino groups such as methylamino, N,N-dimethylamino, butylamino, etc.; aryl groups such as tolyl, phenyl, etc.; aryloxy groups such as phenoxy, naphthoxy, etc.; mercapto group, sulfo group, carboxy group, cyano group, carbamoyl group, sulfamoyl group; amido groups such as acetylamino, benzoylamino, etc.; sulfonyl groups such as methane
• the carboxyl group, sulfo group and phosphoric acid group represented by the G may either be free- acid or form their corresponding salts, and those to form their corresponding salts include inorganic cations including alkali metals such as Na, K, Li; alkaline earth metals such as Ca, Mg; and ammonium; or organic ammoniums such as pyridinium, triethyl ammonium, triethanol ammonium, guanidium, and the like; and further, they may form intramolecular salts.
• alkali metals such as Na, K, Li
• alkaline earth metals such as Ca, Mg
• ammonium or organic ammoniums such as pyridinium, triethyl ammonium, triethanol ammonium, guanidium, and the like; and further, they may form intramolecular salts.
• the compound having Formula 7, which is applicable to this invention, according to selection of the Y, is classified as mercapto-substituted anionic derivatives (7-1), pseudothiuronium intramolecular salt derivatives (7-II) and disulfide derivatives (7-111).
• mercapto-substituted anionic derivatives (7-1) mercapto-substituted anionic derivatives (7-1), pseudothiuronium intramolecular salt derivatives (7-II) and disulfide derivatives (7-111).
• the following are typical examples of these compounds:
• the pseudothiuronium intramolecular salt derivative (7-II) can be obtained by effecting addition reaction in a water-soluble solvent such as, e.g., methanol, ethanol, water-containing ethanol, etc., in accordance with the following scheme:
• the sulfide derivative (7-1), part of the compound of this invention, is synthesized by hydrolyzing in a moderate alkaline atmosphere the compound (7-II) shown in the above scheme; to be concrete, can be isolated as a guanidium salt by heating the compound (7-II) in an aqueous ammonium solution.
• the guanidium salt may be converted into an arbitrary salt by being sujected to ion exchange treatment or salt exchange operation.
• the L 1 to L 4 , J 1 and J 2 , Z, G, k, I, m, n, p, q and r are all as defined in the foregoing Formula 7; the s 1 and s 2 each is an integer of 1; and s 3 is an integer of 2.
• the Nu represents a nucleophilic group such as. e.g., a chlorine atom, bromine atom, iodine atom, p-toluenesulfonyloxy group, trifluoromethyl-sulfonyloxy group, or the like.
• R 73 and R 74 each represents a hydro gen atom or an alkyl, aryl or heterocyclic group.
• any of these compounds having Formula 7 may be incorporated either into a light-sensitive material or into a developer solution.
• the compound is allowed into all the photographic layers including silver halide emulsion layers, and its adding amount is preferably from 1 ⁇ 10 -7 to 1 ⁇ 10 -3 mole per m 2.
• its suitable adding amount is from 1 ⁇ 10 -1 to 1 ⁇ 10 -3 mole per liter.
• the incorporation of the compound is carried out generally in the manner that it is dissolved into water or an organic solvent arbitrarily miscible with water, such as methanol, ethanol, etc., and the solution is then added.
• the silver halide emulsion which is applicable to this invention may be made color-sensitive to desired wavelength regions by using sensitizing dyes.
• sensitizing dyes include those commonly available ones including methine dyes and styryl dyes, such as cyanines, hemicyanines, rhodacyanines, merocyanines, oxonols, hemioxonols and the like.
• R ⁇ 1 and R 82 each represents a substitutable alkyl group, provided that at least one of the R 81 and R 82 is a sulfoalkyl or carboxyalkyl group;
• Z is an alkyl or aralkyl group;
• U, V, W and Y each is a hydrogen atom, halogen atom or substitutable alkyl group, substitutable alkoxy group, substitutable alkoxycarbonyl group, carboxyl group or hydroxyl group,
• X- is an acid anion; and
• m is an integer of 1 or 2, provided that the m is when an intramolecular salt is formed.
• Examples of the substituent to the alkyl group represented by the R S1 or R 82 include hydroxyl group, sulfo group, sulfonate group, carboxyl group and salts thereof; halogen atoms such as fluorine atom, chlorine atom, etc.; substituted or unsubstituted alkoxy groups having from 1 to 4 carbon atoms, which may be further substituted by a sulfo group, hydroxyl group, etc.; alkoxycarbonyl groups having from 2 to 5 carbon atoms; alkylsulfonyl groups having from 1 to 4 carbon atoms: sulfamoyl group; substituted or unsubstituted carbamoyl groups including carbamoyl groups substituted by an alkyl group having from 1 to 4 carbon atoms; phenyl groups substituted by, e.g., a sulfo group, carboxyl group, hydroxyl group, etc.; vinyl group; and the like.
• Examples of the unsubstituted alkyl group include methyl, ethyl, propyl and butyl groups.
• Examples of the substituted alkyl group include hydroxyalkyl groups such as 2-hydroxyethyl, 3-hydroxypropyl, etc.; sulfoalkyl groups such as 2-sulfoethyl, 3-sulfopropyl, 3-sulfobutyl, 4-sulfobutyl, 2-hydroxy-3-sulfopropyl, 2-chloro-3-sulfopropyl, etc.; carboxyalkyl groups such as carboxymethyl carboxyethyl, carboxypropyl, etc.; 2,2,2-trifluoroethyl group; 2-(3-sulfopropyloxy)ethyl group; 2-(2-hydroxyethoxy)ethyl group; ethoxycarbonylethyl group; methylsulfonylethyl group; sulfamoylalkyl
• the halogen atom represented by the U, V, W or Y is, e.g., a fluorine atom, chlorine atom, bromine atom, or the like.
• the alkyl group is, e.g., a methyl, ethyl, propyl. butyl or the like group.
• the alkoxy group is, e.g., a methoxy, ethoxy, propoxy, butoxy or the like group.
• the alkoxycarbonyl group is, e.g., a methoxycarbonyl, ethoxycarbonyl or the like group. Each of these groups may be substituted by a halogen atom, sulfo group, hydroxyl group, carboxy group, or the like.
• the alkyl group represented by the Z is, for example, a methyl, ethyl or propyl group.
• the aralkyl group represented by the Z is, e.g., a benzyl group.
• the acid anion represented by the X- is, for example, a chloride, bromide, iodide, thiocyanate, sulfonate, methyl sulfonat, ethyl sulfonate, perchlorate, p-toluene-sulfonate. or the like.
• R 91 , R 92 and R 93 each represents a substitutable alkyl group
• U , V , W and Y each represents a hydrogen atom, halogen atom, trifluoromethyl group, cyano group, carboxyl group, alkoxy group, alkoxycar- ponyl group, hydroxyl group, acyloxy group, hydroxyalkyl group, hydroxyalkoxy group or phenyl group
• X-s an acid anion
• n is an integer of 1 or 2, provided that the n is 1 when an intramolecular salt is ormed.
• the alkyl group represented by the R 91 , R 92 or R 93 is as defined in the alkyl group of the R 81 or R 82 of Formula 8.
• the alkoxy group represented by the U', V', W or Y is, for example, a methoxy group, ethoxy group, propoxy group or butoxy group;
• the alkoxycarbonyl group is, for example, a methoxycarbonyl group, ethoxycarbonyl group, or the like;
• the acyloxy group is, for example, an acetyloxy group, propionyloxy group or the like;
• the hydroxyalkyl group is, e.g., a hydroxymethyl group, hydroxyethyl group, hydrox- propyl group, hydroxybutyl group or the like;
• the hydroxyalkoxy group is, e.g., a hydroxymethoxy group, hydroxyethoxy group, hydroxypropoxy group, hydroxybutoxy group or the like.
• the acid anion represented by the X- is as defined in the X- of Formula 8.
• R 101 , R 102 , R 103 and R 104 each represents a substitutable alkyl group;
• U, V, W and Y each represents a hydrogen atom, halogen atom, substitutable alkyl group, substitutable alkoxy group, substitutable alkoxycarbonyl group, carboxyl group, hydroxyl group, cyano group or substitutable acyloxy group.
• the alkyl group represented by the R 101 , R 102 , R 103 or R 104 is as defined in that of the R 81 or R 82 of Formula 8; the halogen atom, alkyl group, alkoxy group and alkoxycarbonyl group represented by the U, V, W or Y are as defined in the U or Y of Formula 8; the acyloxy group is as defined in the U or Y of Formula 9; and 1 is an integer of 1 or 2.
• the acid anion represented by the X- is as defined in the X - of Formula 8.
• sensitizing dyes having Formulas 8 through 10 are of the prior art, and may be easily synthesized by those methods of the prior art; for example, in accordance with those methods as described in the literature cited in, e.g., F. M. Homes, 'The Cyanine Dyes and Related Compounds,' Interscience Publishers, New York (1964).
• R 111 is an alkyl group, particularly an alkyl group having from 1 to 8 carbon atoms, which is preferably a methyl, ethyl, 2-hydroxyethyl, 2-methoxyethyl, 2-acetoxyethyl, carboxymethyl, 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, sulfoethyl, 3-sulfopropyl, 3-sulfobutyl, 4-sulfobutyl, vinylmethyl, benzyl, phenethyl, n-propyl, isopropyl, n-butyl or the like group.
• Z is a group of non-metal atoms necessary to form a 5- or 6-member heterocyclic ring, such as, e.g., a thiazole ring, selenazole ring, oxazole ring, benzothiazole ring, benzoselenazole ring, benzoxazole ring, naphthothiazole ring, naph- thoselenazole ring, naphthoxazole ring, pyridine ring, quinoline ring, or the like.
• Each heterocyclic ring may have a substituent such as, e.g., a halogen atom such as chlorine, bromine, etc.; an alkyl group, preferably an alkyl group having from 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, etc.; a halogenated alkyl group such as trifluoromethyl; an alkoxy group, preferably an alkoxy group having from 1 to 4 carbon atoms, such as methoxy, ethoxy, n-propyloxy, etc.; a hydroxy group; an aryl group such as phenyl; or the like.
• a substituent such as, e.g., a halogen atom such as chlorine, bromine, etc.
• an alkyl group preferably an alkyl group having from 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, etc.
• a halogenated alkyl group
• Q is a group of nonmetal atoms necessary to form a 5-member cyclic ring such as a rhodanine ring, thiohydantoin ring, thiooxazolidine-di-one ring, thioselenalidine-di-one ring or the like.
• Each of these heterocyclic rings may have a substituent such as an alkyl group preferably an alkyl group having from 1 to 8 carbon atoms, such as methyl, ethyl, n-propyl, 2-hydroxyethyl, 2-hydroxyethyloxyethyl, 2-methoxyethyl, 2-acetoxyethyl, carboxymethyl, 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, 2-sulfoethyl, 3-sulfopropyl, 3-suffobutyt, 4-sulfobutyl, benzyl, phenethyl, n-propyl, n-butyl, etc.; an aryl group such as phenyl, p-sulfophenyl, etc.; pyridyl group such as 2-pyridyl, 3-pyridyl, 4-pyridyl, 4-methyl-2-pyridyl, etc.
• Examples of the compound having Formula 11 include, for example, the following Compounds 11-1 through 11-25:
• Incorporation/dispersion of any of these sensitizing dyes of Formulas 8 through 11, applicable to this invention, into a silver halide emulsion may be carried out in accordance with various methods of the prior art, such as, for example, those methods of dispersing sensitizing dyes along with a surface active agent as described in Japanese Patent Examined Publication No. 44895/1974 and Japapnese Patent O.P.I. Publication No. 11419/1975 those methods of adding sensitizing dyes in the form of a dispersed product with a hydrophilic substrate as described in Japanese Patent O.P.I. Publication Nos. 16624/1978, 102732/1978, 102733/1978, U.S. Patent Nos.
• the adding amount of these sensitizing dyes having Formulas 8, 9 and 10, usable in this invention is an amount necessary for the spectral sensitization of a silver halide emulsion, such as, e.g., 10- 5 to 2x10- 2 mole per mole of silver halide, and more preferably from 10- 4 to 2x10- 3 mole.
• the silver halide photographic emulsion of the light-sensitive material to be used in this invention may contain a hardening agent, examples of which include those commonly usable as hardening agents; aldehydes such as formaldehyde, glyoxal, glutaraldehyde, mucochloric acid, etc.; N-methylol compounds such as dimethylol urea, methylol-dimethylhydantoin, etc.; dioxane derivatives such as 2,3-dihydroxydioxane, etc.; active vinyl compounds such as 1,3,5-triacryloyl-hexahydro-s-triazine, bis(vinylsulfonyl)methyl ether, etc.; active halogen compounds such as 2,4-dichloro-6-hydroxy-s-triazine, etc.; and the like. These may be used alone or in combination.
• the emulsion may also use those commonly applicable additives such as a viscosity increasing agent
• the light-sensitive material of this invention may, according to purposes, contain ordinary additives such as couplers, ultraviolet absorbing agent, brightening agent, image stabilizer, oxidation inhibitor, lubricant, sequestering agent, dispersing agent, and the like.
• the light-sensitive material for use in the method of this invention may have non-silver-halide-emulsion layers such as a protective layer, intermediate layers, filter layers, antihalation layer, subbing layer, auxiliary layers, antiirradiation layer, and the like.
• non-silver-halide-emulsion layers such as a protective layer, intermediate layers, filter layers, antihalation layer, subbing layer, auxiliary layers, antiirradiation layer, and the like.
• baryta paper, polyethylene- laminated paper, cellulose acetate film, cellulose nitrate film, polyethylene terephthalate film and the like may be arbitrarily selected according to the purpose for which the light-sensitive material is used.
• the light-sensitive silver halide emulsion layer and other layers coated on the support may contain a homo- or copolymer latex comprised of an alkyl acrylate, alkyl methacrylate, acrylic acid, glycidyl acrylate, etc., for the purpose of improving the dimensional stability of layers' physical property of the light-sensitive material.
• the light-sensitive silver halide emulsion may contain a stabilizer or antifoggant such as 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene, 1-phenyl-5-mercaptotetrazole, resolcinol-oxime, hydroiquinone-aldoxime or any of various other equivalent compounds, which may be added in an amount of from 10- 4 to 10- 1 mole per mole of silver halide.
• a stabilizer or antifoggant such as 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene, 1-phenyl-5-mercaptotetrazole, resolcinol-oxime, hydroiquinone-aldoxime or any of various other equivalent compounds, which may be added in an amount of from 10- 4 to 10- 1 mole per mole of silver halide.
• Silver iodobromide grains containing 1.5 mole% silver iodide were prepared, which were cubic grains having an average grain size of 0.30 um.
• the silver halide grains were subjected to both gold sensitization and sulfur sensitization, then to this emulsion were added a sensitizing dye and a stabilizer 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene, and then the emulsion was divided into 13 parts so that each part contains 1 mole of silver halide.
• To these parts of the emulsion were added 3-pyrazolidone compounds and di- or tri- hydroxybenzene-type compounds of the kinds and in the amounts specified in Table 4, and further were added saponin, formalin and glyoxal.
• each of these emulsions was coated on a polyethylene terephthalate support so that the coating weight of the silver was 4.5g/m 2 , and over this emulsion layer was coated a gelatin protective layer so that the coating weight of the gelatin was 1.8g/m 2 , and the layers were dried, whereby light-sensitive material samples were obtained.
• Each sample was cut into a small piece, and the piece was exposed for 20 seconds through a step wedge with a contact screen for negative use (100 lines per inch) attached to its one side to a tungsten light.
• This sample was processed for 30 seconds at 35 C in the following developer solution and fixing solution by using KONICA Automatic Processor GR-27 (manufactured by KONICA CORPORATION).
• each of the thus processed samples was measured by means of a KONICA Digital Densitometer PDP-65, and the sensitivity of each sample was expressed as a relative speed to the Sample No.1's sensitivity obtained at a density point of 3.0, which was regarded as 100, and further the tangent to the line between the density points of 0.3 and 3.0 was expressed as the gamma of each sample. Also, evaluation of the halftone dot quality of each sample was made in the manner of visual observation through a 100-power magnifier and by rating the quality on the basis of 10-grade evaluation system, in which those dots with their periphery having little or no fringe and being smooth are rated Grade 10, while those dots with their periphery having much fringe and being jagged are rated Grade 1.
• An emulsion containing silver chlorobromide grains comprised of 65 mole% silver chloride and 35 mole% silver bromide was prepared. This emulsion was used to prepare Samples No.21 to No.31 in the same manner as in Example 1 except that compounds of Formulas 4, 5 and 6 were used in combination with the hydrazide compounds of this invention.
• Example 5 The obtained samples were evaluated int he same manner as in Example 1.
• the compositions and the evaluated results of the respective samples are given in Table 5.

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