EP0452772B1 - Matériaux photographiques à l'halogénure d'argent - Google Patents

Matériaux photographiques à l'halogénure d'argent Download PDF

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Publication number
EP0452772B1
EP0452772B1 EP19910105559 EP91105559A EP0452772B1 EP 0452772 B1 EP0452772 B1 EP 0452772B1 EP 19910105559 EP19910105559 EP 19910105559 EP 91105559 A EP91105559 A EP 91105559A EP 0452772 B1 EP0452772 B1 EP 0452772B1
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Prior art keywords
group
substituted
groups
unsubstituted
silver halide
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EP19910105559
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German (de)
English (en)
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EP0452772A1 (fr
Inventor
Senzo Sasaoka
Morio Yagihara
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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Priority claimed from JP2094551A external-priority patent/JPH0367243A/ja
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/42—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
    • 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

Definitions

  • the present invention concerns silver halide photographic materials and, in particular, it concerns sensitive materials which can be used in fields such as X-ray, photographic plate making, micro and general purpose amateur negative films, for example.
  • the present invention concerns silver halide photographic materials which exhibit improved resistance to the slip-fogging and pressure sensitization which sometimes arise when films are rubbed together.
  • Increased covering power is essential to increase the speed of X-ray photosensitive materials, micro-photosensitive materials and general purpose amateur negative photosensitive materials, for example; and it is known that the covering power is increased by reducing the amount of gelatin using the methods disclosed, for example, in JP-A-61-116347 and JP-A-57-182732 (the term "JP-A” as used herein refers to a "published unexamined Japanese patent application").
  • JP-A blackening of abraded parts may occur when films are rubbed together if the amount of gelatin with respect to silver is reduced, and slip-fogging may occur as well.
  • Hydroquinone derivatives are used in JP-A-62-21143, JP-A-56-1936 and JP-A-54-40629, but these are different compounds from those represented by formula (I) of the present invention.
  • DE-A-2 758 765 discloses photographic materials comprising at least one hydrophilic layer containing a hydrazine derivative and a substituted hydroquinone derivative but does not disclose a benzotriazole which accelerates the adsorption on the surface of the silver halide grains.
  • GB-A-2 077 453 discloses photographic materials containing an indazole-substituted hydroquinone and hydrazine in the silver halide photographic emulsion layer.
  • This prior art document discloses 6-methyl-2-(5-nitro-2-indazolyl)hydroquinone which however shows no effect on the abrasion and if further the addition amount of this compound is increased, the photographic speed is reduced.
  • the object of the present invention is to provide silver halide photographic materials with which the problems of the conventional technology outlined above are overcome. These materials exhibit improved resistance to abrasion during handling and blackening due to pressure, have high photographic speed and are suitable for rapid processing.
  • a silver halide photographic material comprising a support having thereon at least one of a surface latent image silver halide emulsion layer and other hydrophilic colloid layers, wherein said at least one of an emulsion layer and other hydrophilic colloid layers contains a compound represented by formula (I): wherein X represents -OR 1 or R 1 represents a hydrogen atom or a group capable of being converted to a hydrogen atom on hydrolysis; R 2 , R 3 and R 4 , which may be the same or different, each represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted oder unsubstituted aryl group, a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, a substituted or unsubstituted alkylcarbonyl group, a substituted or unsubstituted
  • the group which can become a hydrogen atom by hydrolysis is, for example, a -COR 7 group (where R 7 represents a substituted or unsubstituted alkyl group having from 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having from 6 to 20 carbon atoms or a substituted or unsubstituted amino group having from 1 to 20 carbon atoms) or a group (where J represents or -SO 2 , and Z represents a plurality of atoms required to form at least one 5- or 6-membered heterocyclic ring).
  • the substitutable groups represented by R 2 , R 3 and R 4 can be, for example, halogen atoms (fluorine, chlorine, bromine), alkyl groups (preferably having 1 to 20 carbon atoms), aryl groups (preferably having 6 to 20 carbon atoms), alkoxy groups (preferably having 1 to 20 carbon atoms), aryloxy groups (preferably having 6 to 20 carbon atoms), alkylthio groups (preferably having 1 to 20 carbon atoms), arylthio groups (preferably having 6 to 20 carbon atoms), acyl groups (preferably having 2 to 20 carbon atoms), acylamino groups (preferably alkanoylamino groups having 1 to 20 carbon atoms and benzoylamino groups having 6 to 20 carbon atoms), nitro groups, cyano groups, oxycarbonyl groups (preferably alkoxycarbonyl groups having 1 to 20 carbon atoms and aryloxycarbonyl groups having 6 to 20 carbon atoms), carboxyl groups, sulfo groups, ureid
  • R 2 , R 3 and R 4 may be the same or different, or in cases where any two of R 2 , R 3 and R 4 are substituted onto adjacent carbon atoms of the benzene ring, they may be joined together to form a 5- to 7-membered carbocyclic or heterocyclic ring, and these rings may be saturated or unsaturated.
  • ring compounds formed include cyclopentane, cyclohexane, cycloheptane, cyclopentene, cyclohexadiene, cycloheptadiene, indane, norbornane, norbornene and pyridine, and the ring compounds may have further substituent groups.
  • R 2 , R 3 and R 4 each preferably contain from 1 to 10 carbon atoms in total.
  • R 5 and R 6 each represents hydrogen atoms, substituted or unsubstituted alkyl groups, substituted or unsubstituted aryl groups, substituted or unsubstituted alkylsulfonyl groups, substituted or unsubstituted arylsulfonyl groups, substituted or unsubstituted alkylcarbonyl groups, substituted or unsubstituted arylcarbonyl groups or substituted or unsubstituted carbamoyl groups, and R 5 and R 6 may be the same or different, and they may be joined together to form a nitrogen-containing heterocyclic ring (for example, a morpholine group, a piperidine group, a pyrrolidine group, an imidazolyl group, a piperazino group may be formed).
  • a nitrogen-containing heterocyclic ring for example, a morpholine group, a piperidine group, a pyrrolidine group, an imidazolyl group,
  • R 5 and R 6 each is most preferably hydrogen atoms.
  • X is preferably substituted in the ortho or para position with respect to the -OR 1 group and, of the groups which can be represented by X, the -OR 1 groups are preferred, and R 1 is most preferably a hydrogen atom.
  • Y is a group which promotes adsorption on silver halide
  • L is a divalent linking group.
  • m is 0 or 1.
  • Preferred examples of groups which promote adsorption on silver halide, represented by Y, include the thioamido group, the mercapto group, groups which have a disulfide bond and nitrogen-containing heterocyclic groups.
  • the heterocyclic mercapto groups which may be represented by Y may be the same as the cyclic thioamide groups to which they are related tautomerically in those cases where there is a nitrogen atom adjacent to the carbon atom to which the -SH group is bonded, and examples of these groups are 4-thiazolin-2-thione, 4-imidazolin-2-thione, 2-thiohydantoin, rhodanine, thiobarbituric acid, tetrazolin-5-thione, 1,2,4-triazolin-3-one, 1,3,4-thiadiazolin-2-thione, 1,3,4-oxadiazolin-2-thione, benzimidazolin-2-thione, benzoxazolin-2-thione and benzothiazolin-2-thione, and these may be further substituted with substituent groups.
  • the nitrogen-containing 5- or 6-membered heterocyclic rings represented by Y are comprised of combinations of nitrogen, oxygen, sulfur and carbon. From among these, preferred examples include benzotriazole, triazole, tetrazole, indazole, benzimidazole, imidazole, benzothiazole, thiazole, benzoxazole, oxazole, thiadiazole, oxadiazole and triazine. These mey be further substituted with appropriate substituent groups. Those listed as possible substituent groups for R 2 , R 3 and R 4 can be cited as substituent groups for these nitrogen-containing compounds as well.
  • the cyclic thioamide groups (mercapto substituted nitrogen-containing heterocyclic groups, for example, 2-mercaptothiadiazole group, 3-mercapto-1,2,4-triazole group, 5-mercaptotetrazole group, 2-mercapto-1,3,4-oxadiazole group and 2-mercaptobenzoxazole group) or the benzotriazole group are preferred.
  • Two or more Y-(L) m - groups may be substituted, and these groups may be the same or different.
  • the divalent linking groups represented by L are atoms or groups of atoms containing at least one atom selected from C, N, S and O.
  • These groups may be substituted with appropriate substituent groups, such as those described above for R 2 , R 3 and R 4 .
  • the melting point of the obtained compound was 256-257°C.
  • the compounds represented by formula (I) are included in photographic materials in amounts of preferably from 1 ⁇ 10 -5 mol to 1 ⁇ 10 -1 mol, and more preferably from 1 ⁇ 10 -4 mol to 5 ⁇ 10 -2 mol, per mol of silver halide.
  • Hydrazine compounds are also used in the present invention.
  • the hydrazine derivatives which are used are those represented by formula (II) indicated below
  • R 1 ' represents an aliphatic group or an aromatic group
  • R 2 ' represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group or a hydrazino group
  • G 1 represents a group, an -SO 2 - group, an -SO- group, a group, a group, a thiocarbonyl group or an iminomethylene group
  • a 1 and A 2 each represents hydrogen atoms, or one represents a hydrogen atom and the other represents a substituted or unsubstituted alkylsulfonyl group, or a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group.
  • the aliphatic groups represented by R 1 ' in formula (II) preferably have 1 to 30 carbon atoms, and they are most preferably linear chain, branched or cyclic alkyl groups which have 1 to 20 carbon atoms.
  • the alkyl groups may also include substituent groups.
  • the aromatic groups represented by R 1 ' in formula (II) are single ring or double ring aryl groups or unsaturated heterocyclic groups.
  • the unsaturated heterocyclic groups may be condensed with aryl groups.
  • Aryl groups are preferred for R 1 ', and those which contain a benzene ring are especially desirable.
  • the aliphatic groups or aromatic groups represented by R 1 ' may be substituted, and typical substituent groups include, for example, alkyl groups, aralkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, aryl groups, substituted amino groups, ureido groups, urethane groups, aryloxy groups, sulfamoyl groups, carbamoyl groups, alkyl- or arylthio groups, alkyl- or arylsulfonyl groups, alkyl- or arylsulfinyl groups, hydroxyl groups, halogen atoms, cyano groups, sulfo groups, aryloxycarbonyl groups, acyl groups, alkoxycarbonyl groups, acyloxy groups, carboxamido groups, sulfonamido groups, carboxyl groups, phosphonamido groups, diacylamino groups, imide groups and groups.
  • typical substituent groups include, for
  • the preferred substituent groups are, for example, alkyl groups (preferably having 1 to 20 carbon atoms), aralkyl groups (preferably having 7 to 30 carbon atoms), alkoxy groups (preferably having 1 to 20 carbon atoms), substituted amino groups (preferably amino groups substituted with alkyl groups having 1 to 20 carbon atoms), acylamino groups (preferably having 2 to 30 carbon atoms), sulfonamido groups (preferably having 1 to 30 carbon atoms), ureido groups (preferably having 1 to 30 carbon atoms) and phosphonamido groups (preferably having 1 to 30 carbon atoms).
  • the alkyl groups represented by R 2 ' in formula (II) are preferably those having 1 to 4 carbon atoms, and the single ring and double ring aryl groups (for example, those which contain a benzene ring) are preferred as aryl groups.
  • G 1 is a group
  • the preferred groups among those represented by R 2 ' are, for example, hydrogen atoms, alkyl groups (for example, methyl, trifluoromethyl, 3-hydroxypropyl, 3-methanesulfonamidopropyl, phenylsulfonylmethyl), aralkyl groups (for example, o-hydroxybenzyl) and aryl groups (for example, phenyl, 3,5-dichlorophenyl, o-methanesulfonamidophenyl, 4-methanesulfonylphenyl, 2-hydroxymethylphenyl).
  • the hydrogen atom is especially desirable.
  • R 2 ' may also be substituted, and the substituent groups may be substituent groups for on R 1 .
  • G 1 in formula (II) is most preferably a group.
  • R 2 ' may also be a group such that a cyclization reaction occurs, cleaving the G 1 -R 2 ' portion from the rest of the molecule and forming a ring structure which contains the atoms of the -G 1 -R 2 ' portion. Examples include those disclosed, for example, in JP-A-63-29751.
  • R 1 ' or R 2 ' in the formula (II) may have incorporated within them the ballast groups or polymers which are normally used in immobile photographically useful additives such as couplers.
  • Ballast groups are comparatively inert groups with respect to photographic properties which have at least 8 carbon atoms; and examples of the ballast groups include alkyl groups, alkoxy groups, phenyl groups, alkylphenyl groups, phenoxy groups and alkylphenoxy groups.
  • those disclosed, for example, in JP-A-1-100530 can be cited as the above polymers.
  • R 1 ' or R 2 ' in the formula (II) may have incorporated therein groups which intensify adsorption on silver halide grains.
  • absorbing groups include thiourea groups, heterocyclic thioamide groups, mercapto heterocyclic groups and triazole groups disclosed, for example, in US-A-4,385,108 and 4,459,347, JP-A-59-195233, JP-A-59-200231, JP-A-59-201045, JP-A-59-201046, JP-A-59-201047, JP-A-59-201048, JP-A-59-201049, JP-A-61-170733, JP-A-61-270744, JP-A-62-948, JP-A-63-234244, JP-A-63-234246 and JP-A-63-234245.
  • a 1 and A 2 are most preferably hydrogen atoms.
  • hydrazine derivatives which can be used in the present invention include, as well as those indicated above, those disclosed in Research Disclosure , Item 23516 (November, 1983) page 346, and in the literature cited therein, and in US-A-4,080,207, 4,269,929, 4,276,364, 4,278,748, 4,385,108, 4,459,347, 4,560,638 and 4,478,928, GB-B-2,011,391B, JP-A-60-179734, JP-A-62-270948, JP-A-63-29751, JP-A-61-170733, JP-A-61-270744, JP-A-62-948, EP 217,310 or US-A-4,686,167, JP-A-62-178246, JP-A-63-32538, JP-A-63-104047, JP-A-63-121838, JP-A-63-129337, JP-A-63-223744, JP-A-6
  • the hydrazine derivatives are preferably added in amounts within the range from 1 ⁇ 10 -6 mol to 5 ⁇ 10 -2 mol, and most preferably from 1 ⁇ 10 -5 mol to 2 ⁇ 10 -2 mol, per mol of silver halide.
  • these compounds of the formulae (I) and (II) are included in a photographic material, they can be added to a silver halide emulsion solution or to a hydrophilic colloid solution in the form of an aqueous solution if they are soluble in water; or in the form of a solution in an organic solvent which is miscible with water, such as an alcohol (for example, methanol, ethanol), an ester (for example, ethyl acetate) or a ketone (for example, acetone), in cases where the compounds are insoluble in water.
  • an alcohol for example, methanol, ethanol
  • an ester for example, ethyl acetate
  • a ketone for example, acetone
  • the addition can be made at any time from the start of chemical ripening until the solution is coated, but the addition is preferably made after the completion of chemical ripening, and addition to the coating liquid is especially desirable.
  • Methods for the preparation of the silver halide emulsions which can be used in the present invention include the methods described by P. Glafkides in Chimie et Physique Photographique (published by Paul Montel, 1967), by G.F. Duffin in Photographic Emulsion Chemistry (published by the Focal Press, 1966) and by V.L. Zelikman et al. in Making and Coating Photographic Emulsions (published by the Focal Press, 1964), the conversion methods disclosed, for example, in U.S. US-A-2,592,250 and 4,075,020, and the methods for the preparation of core/shell emulsions disclosed, for example, in GB-B-1,027,146.
  • the water-soluble silver salt (aqueous silver nitrate solution) is reacted with the water-soluble halogen salt solution using a single jet method, a double jet method or a combination of these methods.
  • the method in which the pAg value in the liquid phase where the silver halide is formed is kept constant, that is, the controlled double jet method, can also be used as one type of a double jet method.
  • grain growth can also be carried out using "so-called silver halide solvents", such as ammonia, thioether and tetra-substituted thiourea, for example.
  • silver halide solvents such as ammonia, thioether and tetra-substituted thiourea, for example.
  • the silver halide grains in the photographic emulsions used in the present invention can have a comparatively wide grain size distribution, but emulsions which have a narrow grain size distribution are preferred, and those in which 90% of all the grains, either in terms of the weight or number of silver halide grains, are of a grain size within ⁇ 40% of the average grain size are most preferred (emulsions of this type are generally referred to as monodisperse emulsions).
  • the silver halide grains in the photographic emulsion may have a regular crystalline form, such as a cubic or octahedral form, or an irregular form, such as a spherical or plate-like form, or they may have a form which is a composite of these crystalline forms.
  • the silver halide grains may be such that the interior and surface layer are a uniform phase or different phases.
  • Mixtures of two or more silver halide emulsions which have been prepared separately may also be used.
  • Cadmium salts, sulfite, lead salts, thallium salts, iridium salts or complex salts thereof; and rhodium salts or complex salts thereof, for example, may also be present during the formation or physical ripening of the silver halide grains in a silver halide emulsion used in the present invention.
  • the silver halide emulsions used in the present invention may or may not be chemically sensitized.
  • Gold sensitization for example, can be used as a method of chemical sensitization, and combinations of gold sensitization with sulfur sensitization, reduction sensitization and noble metal sensitization methods, for example, can be used.
  • the gold sensitization method is typical of the noble metal sensitization methods.
  • Gold compounds comprising principally gold complex salts are used for this purpose.
  • Complex salts of noble metals other than gold, for example, platinum, palladium and iridium, can also be included. Examples have been disclosed, for example, in US-A-2,448,060 and GB-B-618,061.
  • sulfur compounds which are contained in gelatin
  • various sulfur compounds for example, thiosulfate, thioureas, thiazoles and rhodanines, can be used as sulfur sensitizing agents. Examples have been disclosed in US-A-1,574,944, 2,278,947, 2,410,689, 2,728,668, 3,501,313 and 3,656,955.
  • Stannous salts, amines, formamidinesulfinic acid and silane compounds can be used as reduction sensitizing agents, and examples have been disclosed in US-A-2,487,850, 2,518,698, 2,983,609, 2,983,610 and 2,694,637.
  • the silver halide emulsions can be optically sensitized to increase the photographic speed and to provide photosensitivity to a prescribed wavelength region.
  • Sensitizing dyes such as cyanine dyes and merocyanine dyes, for example, can be used individually or together for optical sensitization purposes, and spectral sensitization and supersensitization can be achieved.
  • Various compounds can be included in the photographic emulsions used in the present invention to prevent the occurrence of fogging during the manufacture, storage or photographic processing of the photosensitive material, or to stabilize photographic performance.
  • Inorganic or organic film hardening agents may be included in the photographic emulsion layers, and/or other hydrophilic colloid layers, of the photographic material of the present invention.
  • chromium salts for example, chrome alum, chromium acetate
  • aldehydes for example, formaldehyde, glyoxal, glutaraldehyde
  • N-methylol compounds for example, dimethylolurea, methyloldimethylhydantoin
  • dioxane derivatives for example, 2,3-dihydroxydioxane
  • active vinyl compounds for example, 1,3,5-triacryloyl-hexahydro-s-triazine, 1,3-vinylsulfonyl-2-propanol
  • active halogen compounds for example, 2,4-dichloro-6-hydroxy-s-triazine
  • mucohalogen acids for example, mucochloric acid, mucophenoxychloric acid
  • Varioue surfactants can be included for various purposes in the photographic emulsion layers, and/or other hydrophilic layers, of a photosensitive material made using the present invention. These compounds may be used, for example, as coating aids or as antistatic agents, to improve slip properties, for emulsification and dispersion purposes, for the prevention of adhesion, and for improving photographic performance (for example, accelerating development, increasing contrast or increasing photographic speed).
  • nonionic surfactants such as saponin (steroid based), alkylene oxide derivatives (for example, polyethylene glycol, polyethylene glycol/polypropylene glycol condensate, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyethylene glycol alkyl amines or amides, and poly(ethylene oxide) adducts of silicones), glycidol derivatives (for example, alkenylsuccinic acid polyglyceride, alkylphenol polyglyceride), fatty acid esters of polyhydric alcohols and sugar alkyl esters; anionic surfactants which include acidic groups, such as carboxylic acid groups, sulfo groups, phospho groups, sulfate ester groups and phosphate ester groups, for example, alkylcarboxylates, alkylsulfonates, al
  • Dispersions of water-insoluble or sparingly soluble synthetic polymers can be included in a photographic emulsion layer and the other hydrophilic colloid layers of the photosensitive material used in the present invention to improve dimensional stability.
  • Processing baths which contain dihydroxybenzene based developing agents as the main developing agent, and p-aminophenol based developing agents or 3-pyrazolidone based developing agents as auxiliary developing agents, are preferably used in the present invention.
  • the dihydroxybenzene based developing agents which can be used in the present invention include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,3-dibromohydroquinone and 2,5-dimethylhydroquinone, for example, but the use of hydroquinone, among these compounds, is especially desirable.
  • Examples of l-phenyl-3-pyrazolidones and derivatives thereof which can be used as auxiliary developing agents include l-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1-p-aminophenyl-4,4-dimethyl-3-pyrazolidone and 1-p-tolyl-4,4-dimethyl-3-pyrazolidone.
  • the p-aminophenol based auxiliary developing agents which can be used in the present invention include N-methyl-p-aminophenol, p-aminophenol, N-( ⁇ -hydroxyethyl)-p-amino phenol, N-(4-hydroxyphenyl)glycine, 2-methyl-p-aminophenol and p-benzylaminophenol, for example; and, among these, N-methyl-p-aminophenol is preferred.
  • a dihydroxybenzene based developing agent in an amount of from 0.05 to 0.8 mol/ liter is preferred.
  • the former are preferably used in amounts of from 0.05 to 0.5 mol/liter and the latter are preferably used in amounts of not more than 0.06 mol/ liter.
  • Sodium sulfite, potassium sulfite, lithium sulfite, sodium bisulfite, potassium metabisulfite and formaldehyde/sodium sulfite can be used as sulfite preservatives in the present invention.
  • the sulfite is used in an amount of at least 0.3 mol/liter; but, if too large an amount is added, it precipitates in the developer and causes contamination of the liquid. So, an upper limit of 1.2 mol/liter is desirable.
  • Tertiary amine compounds and especially the compounds disclosed in US-A-4,269,929, can be included as development accelerators in the developer in the present invention.
  • pH buffers such as boric acid, borax, sodium triphosphate, potassium triphosphate, and the pH buffers disclosed in JP-A-60-93433 can also be used in the developer of the present invention.
  • Development inhibitors such as potassium bromide and potassium iodide
  • organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve, hexylene glycol, ethanol and methanol
  • indazole compounds such as 5-nitroindazole, antifogging agents and black spotting (black pepper) preventing agents, such as 2-mercaptobenzimidazole-5-sulfonic acid sodium salt, and 5-methylbenzotriazole may be included.
  • toners may be included, if desired.
  • surfactants may be included, if desired.
  • hard water softening agents may be included, if desired.
  • film hardening agents may be included, if desired.
  • Well known fixing agent compositions can be used in the present invention.
  • the organic sulfur compounds which are known to be effective as fixing agents can also be used.
  • Water-soluble aluminum salts such as aluminum sulfate and alum, for example, can be included in the fixing solution as film hardening agents.
  • the amount of water-soluble aluminum salt used is generally from 0 to 3.0 g ⁇ Al/liter.
  • ethylenediaminetetraacetic acid ferric complex salts may be used as oxidizing agents.
  • the processing temperature is generally selected within the range from 18°C to 50°C, but temperatures below 18°C and in excess of 50°C may be used.
  • an aqueous solution containing 8.33 g of silver nitrate was added over a period of 26 minutes so the flow rate at the end of the addition was twice that at the start of the addition.
  • 20 ml of 25% ammonia solution and 10 ml of 50% NH 4 NO 3 were added.
  • 240 ml of 1 N sulfuric acid were added after physical ripening of 20 minutes duration, and the mixture was neutralized.
  • an aqueous solution containing 153.34 g of silver nitrate and an aqueous solution of potassium bromide were added over a period of 40 minutes using the controlled double jet method in such a way that the potential was maintained at a pAg value of 8.2.
  • the coating solution described above was coated onto a transparent PET support having a thickness of 175 ⁇ m at the same time as a surface protective layer coating solution.
  • the coated amount of silver was 2.0 g per square meter.
  • the surface protective layer was prepared using the amounts of each component indicated below.
  • the photographic materials 1 to 13 (Table 1) were each obtained in this way.
  • Photographic samples 1 to 13 were subjected to a 1/20th second exposure using green light which had a peak at 550 nm and then they were SP-processed at 35°C (dry to dry time: 45 seconds) using developer RD 7 and fixer Fuji F in an automatic processor FPM9000 made by the Fuji Photo Film Co., Ltd.
  • Photographic speed was expressed by means of the reciprocal of the exposure required to provide a density of fog + 1.0 and the results obtained, taking the speed of photographic material 1 to be 100, are summarized in Table 1.
  • Photographic materials 1 to 13 were equilibrated for 1 hour under conditions of 25°C, 25% RH and then they were rubbed at a speed of 1 cm per second with a commercial nylon brush under the same conditions with a loading of 100 g per 2 ⁇ 1 cm area. The samples were then processed in an unexposed condition in accordance with the automatic processing operation described above and the number of black abrasion lines was counted.
  • a base was prepared with an underlayer with the coated amounts indicated below established on both surfaces of a blue colored poly(ethylene terephthalate) support having a thickness of 175 ⁇ m.
  • Example 1 The emulsions described in Example 1 were coated onto both sides of this base in amounts of 1.9 g/ m 2 of coated silver per side. At this time, the compound of the formula (I), or the comparative compound, was added so the amount added per mol of silver was as shown in Table 2. Protective layers were obtained using the same coating solution as in Example 1. The amount of film hardening agent added was changed to 15 mmol per 100 g of gelatin. Photographic materials 1 to 13 were obtained in this way. Abrasion resistance was evaluated in the same way as described in Example 1. However, processing was modified to that described below for the evaluation of photographic performance.
  • Each processing tank was filled with a processing solution as indicated below when starting development processing.
  • Emulsions A to E were prepared using the methods described below.
  • An aqueous solution of silver nitrate and an aqueous solution containing potassium bromide and potassium iodide were added, using the double jet method, to a container which contained potassium bromide and 25 g of gelatin in 1 liter of water, while maintaining a pAg value of 8.7.
  • a regular octahedral silver iodobromide emulsion of average grain size 0.8 ⁇ m was obtained.
  • This emulsion was chemically sensitized using sodium thiosulfate and chloroauric acid; a regular octahedral photosensitive silver iodobromide emulsion (A), which had an iodide content of 8 mol% at pAg 8.6, pH 6.4, was obtained.
  • An aqueous solution of silver nitrate and an aqueous solution of potassium bromide were added using the double jet method, with the usual ammonia procedure, to a vessel which contained 25 g of potassium bromide, 4.5 g of potassium iodide, 9 ml of 2 N potassium thiocyanate and 24 g of gelatin in 1 liter of water.
  • This emulsion was chemically sensitized using sodium thiosulfate and chloroauric acid; the photosensitive silver iodobromide emulsion (B) having pAg 8.6, pH 6.4 was obtained.
  • Photosensitive silver iodobromide emulsion (C) average grain size 0.6 ⁇ m, which contained 6 mol% of iodide, was obtained by including 9 g of potassium iodide in the initial solution and carrying out grain formation and chemical sensitization in the same way as described for emulsion (B).
  • An aqueous solution of silver nitrate and a mixed aqueous solution of potassium bromide and potassium iodide were prepared. 5% of the volume of the aqueous solution of silver nitrate and the mixed aqueous solution were added to a vessel which contained 5 g of potassium bromide and 30 g of gelatin in 1 liter of water in such a way that the pAg value was maintained at 9.5. Then, 5% of the volume of the silver nitrate solution were added using the siagle jet method; and finally the remaining 90% of the aqueous silver nitrate solution and the mixed aqueous solution of potassium bromide and potassium iodide were added using the double jet method, maintaining a pAg value of 8.1.
  • a tabular silver halide emulsion of average projected area diameter 1.3 ⁇ m, standard deviation 15% and average aspect ratio 6.5 was obtained.
  • This emulsion was chemically sensitized using sodium thiosulfate and chloroauric acid; and the photosensitive silver iodobromide emulsion (E), which had an iodide content of 3 mol%, was obtained at pAg 8.6 and pH 6.4.
  • Coated samples were prepared by coating the emulsion layer formulation indicated below onto the emulsion layer coating side of a triacetyl cellulose support having a subbing layer on the emulsion coating side, and on the reverse side, a backing layer having the following formulation: Emulsion Layer Formulation Coated silver amount 3.5 g/m 2 Weight of gelatin 1.5 g/g-Ag 4-Hydroxy-6-methyl-1,3,3a,7-tetra-azaindene 10 mg/g-Ag Poly(ethylene oxide) 8 mg/g-Ag Poly(potassium p-vinylbenzenesulfonate) 20 mg/g-Ag Sensitizing Dye 230 mg/mol-Ag
  • the compounds of the formula (I) and comparative compounds were added in the amounts shown in Table 3. Hard films were prepared after storing the coated samples for 7 days at 25°C, 65% RH by means of bis(vinylsulfonylacetamido)ethane so the film thickness on immersion for 3 minutes in distilled water at 25°C was 200 ⁇ 10% of the dry film thickness.
  • Coated samples 1 to 25 were stored for 7 days under conditions of 25°C, 65% RH. The samples were then exposed for 1/100 second using a filter which had a wavelength distribution corresponding to sunlight, after which they were developed for 7 minutes at 20°C with the developer; then, after fixation with the fixer, the samples were washed with water and dried. The photographic speeds were measured at fog + 0.3 density using the processed samples.
  • the photographic speeds of each of the emulsions A to E were compared as relative value obtained by taking the speed of the blank in each case to be 100.
  • Abrasion was carried out with a nylon brush using the same method as described in Example 1.
  • the sample was developed and processed in the same way, with sensitometry. Then, the number of blackened abrasion lines was counted in the same way as described in Example 1.
  • the samples of the present invention exhibited increased contrast in the toe part (so-called toe cutting) in the sensitometry; and a development accelerating effect was also observed when the development time was short.
  • Coated samples 1 to 11 were prepared with the layer constitution indicated below.
  • Third Layer Gelatin 0.4 g/m 2 Poly(potassium p-vinylbenzenesulfonate) 5 mg/m 2
  • Fifth Layer (using Emulsion D) Amount of silver 4.6 g/m 2
  • Poly(potassium p-vinylbenzenesulfonate) 88 mg/m 2
  • Hard films were prepared after storing the coated samples for 7 days at 25°C, 65% RH. Bis(vinylsulfonylacetamido)ethane was used to ensure that the film thickness, after immersion for 3 minutes in distilled water at 25°C, was 300 ⁇ 10% with respect to the dry film thickness.
  • Emulsions (C) and (D) had 230 mg/mol-Ag of the same dye as in Example 3 added before post ripening.
  • An aqueous solution of silver nitrate and an aqueous solution containing potassium bromide and potassium iodide were mixed using the double jet method in the presence of ammonia while maintaining a pAg value of 7.9.
  • a monodisperse cubic silver iodobromide emulsion was prepared, having average grain size of 0.2 ⁇ m (silver iodide 2.0 mol%, silver bromide 98.0 mol%).
  • the sensitizing dye 5,5'-dichloro-3,3'-di(3-sulfopropyl)-9-ethyl-oxacarbocyanine sodium salt was added in an amount of 6 ⁇ 10 -4 mol per mol of silver to spectrally sensitize the emulsion.
  • An aqueous gelatin solution comprised of gelatin, sodium dodecylbenzenesulfonate, silicone oil, fluorine based surfactant, colloidal silica, poly(ethyl acrylate) dispersion, poly(methyl methacrylate) (particle size: 2.5 ⁇ m) matting agent and poly(sodium styrenesulfonate) thickener was coated as a protective layer to provide a coated gelatin amount of 1.6 g/m 2 .
  • the emulsion layer and the protective layer were coated simultaneously in such a way that the emulsion provided a coated silver amount of 3.6 g/m 2 .
  • the two samples were exposed for 5 seconds through an optical wedge for sensitometric purposes using tungsten light (color temperature: 3,200K). Then, they were developed for 30 seconds at 38°C in a developer having the composition indicated below, fixed, washed with water and dried. (An automatic processor, model FG-660F, made by the Fuji Photo Film Co., Ltd. was used for development processing.)
  • the photographic speed was read off from the exposure at the point of fog + density 1.5 on the characteristic curve.
  • the gamma value was obtained as the gradient of the straight line drawn between the point of fog + density 0.3 and the point of fog + density 3.0 on the characteristic curve.
  • a gamma value of at least 10 is desirable to ensure adequate image quality.
  • a silver chloroiodobromide emulsion (silver iodide content: 0.1 mol%, silver bromide content: 30 mol%) was prepared using the double jet method.
  • (NH 4 ) 3 RhCl 6 was added as a rhodium salt to the aqueous halogen solution in an amount of 1 ⁇ 10 -7 mol/mol-Ag in the silver chloroiodobromide emulsion.
  • K 3 IrCl 6 an iridium salt, was also added to the aqueous halogen salt at the same time in an amount of 4 ⁇ 10 -7 mol/mol-Ag.
  • the aqueous halogen solution and the aqueous silver nitrate solution were mixed at 45°C over a period of 60 minutes and a monodisperse cubic emulsion having an average grain size of 0.25 ⁇ m was obtained.
  • the compound indicated below was added in an amount of 1.2 ⁇ 10 -3 mol/mol-Ag as a hydrazine compound.
  • the compound of the formula (I) or hydroquinone was added in the amount shown in Table 6.
  • An aqueous gelatin solution comprised of gelatin, sodium dodecylbenzenesulfonate, silicone oil, fluorine based surfactant, colloidal silica, a dispersion of poly(ethyl acrylate), polyacrylamide (molecular weight: 5,000), poly(methyl methacrylate) (particle size: 2.5 ⁇ m), matting agent and poly(sodium styrenesulfonate), thickener, was coated as a protective layer so that the coated amount of gelatin was 1.6 g/m 2 .
  • the emulsion was coated so that the coated amount of silver was 3.6 g/m 2 .
  • the emulsion layer and the protective layer were coated simultaneously.
  • the compounds of the formula (I) used in the present invention performed better with respect to loss of photographic speed, decrease in gamma and abrasion than the comparative compound hydroquinone.

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Claims (3)

  1. Matériau photographique à l'halogénure d'argent comprenant un support sur lequel se trouve au moins une couche parmi une couche d'émulsion d'halogénure d'argent à image latente de surface et d'autres couches de colloïdes hydrophiles, dans lequel ladite ou lesdites couches parmi une couche d'émulsion et d'autres couches de colloïdes hydrophiles contiennent un composé représenté par la formule (I) :
    Figure imgb0088
     dans laquelle X représente

            -OR1

    ou
    Figure imgb0089
     R1 représente un atome d'hydrogène ou un groupe capable d'être converti en un atome d'hydrogène par hydrolyse; R2, R3 et R4, qui peuvent être identiques ou différents, représentent chacun un atome d'hydrogène ou un groupe substituant, R5 et R6, qui peuvent être identiques ou différents, représentent chacun un atome d'hydrogène, un groupe alkyle substitué ou non substitué, un groupe aryle substitué ou non substitué, un groupe alkylsulfonyle substitué ou non substitué, un groupe arylsulfonyle substitué ou non substitué, un groupe alkylcarbonyle substitué ou non substitué, un groupe arylcarbonyle substitué ou non substitué ou un groupe carbamoyle substitué ou non substitué ; Y représente un groupe hétérocyclique à 5 ou 6 chaînons ayant un groupe mercapto ou un groupe benzotriazole contenant une structure > NH; L représente un élément choisi dans le groupe consistant en un groupe alkylène divalent, un groupe alcénylène divalent, un groupe alcynylène divalent, un groupe arylène divalent, -NH-, -N=, -CO-, -SO2-, et des combinaisons de ceux-ci ; et m représente 0 ou 1 ;
    et dans lequel ladite ou lesdites couches d'émulsion ou autres couches de colloïdes hydrophiles contenant un composé représenté par la formule (I) contiennent aussi un composé représenté par la formule (II) en une quantité de 1x10-6 à 5 x 10-2 mol/mol d'halogénure d'argent :
    Figure imgb0090
     où R1' représente un groupe aliphatique ou un groupe aromatique, R2' représente un atome d'hydrogène, un groupe alkyle substitué ou non substitué, un groupe aryle substitué ou non substitué, un groupe alcoxy substitué ou non substitué, un groupe aryloxy substitué ou non substitué, un groupe amino substitué ou non substitué ou un groupe hydrazino substitué ou non substitué ; G1 représente
    Figure imgb0091
     un groupe thiocarbonyle ou un groupe iminométhylène, et A1 et A2 représentent chacun un atome d'hydrogène, un groupe alkylsulfonyle substitué ou non substitué, un groupe arylsulfonyle substitué ou non substitué ou un groupe acyle substitué ou non substitué, à condition qu'au moins l'un des symboles A1 et A2 représente un atome d'hydrogène et que R1' ou R2' contienne un groupe ballast ou un groupe qui accélère l'adsorption du composé de formule (II) sur la surface des grains d'halogénure d'argent.
  2. Matériau photographique à l'halogénure d'argent selon la revendication 1, dans lequel ledit composé représenté par la formule (I) est ajouté en une quantité de 1 x 10-5 à 1 x 10-1 mol/mol d'halogénure d'argent.
  3. Matériau photographique à l'halogénure d'argent selon la revendication 1, dans lequel ledit composé représenté par la formule (II) est ajouté en une quantité de 1 x 10-6 à 5 x 10-2 mol/mol d'halogénure d'argent.
EP19910105559 1990-04-10 1991-04-09 Matériaux photographiques à l'halogénure d'argent Expired - Lifetime EP0452772B1 (fr)

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JP94551/90 1990-04-10
JP2094551A JPH0367243A (ja) 1989-05-15 1990-04-10 ハロゲン化銀写真感光材料

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DE69121048T2 (de) * 1990-10-23 1997-01-09 Fuji Photo Film Co Ltd Photographisches lichtempfindliches Silberhalogenidmaterial
JP2641982B2 (ja) * 1990-11-19 1997-08-20 富士写真フイルム株式会社 ハロゲン化銀写真感光材料
EP0782042B1 (fr) 1995-12-27 1999-12-01 Fuji Photo Film Co., Ltd. Composé d'hydrazine et matériau photographique à l'halogénure d'argent le contenant
US6100020A (en) * 1997-09-19 2000-08-08 Eastman Kodak Company Process for the preparation of silver halide photographic element
EP0965880B1 (fr) 1998-06-19 2003-03-05 Tulalip Consultoria Comercial Sociedade Unipessoal S.A. Elément photographique ayant rapport rapidité : Dmin amélioré et procédé pour sa fabrication
JP2007041376A (ja) 2005-08-04 2007-02-15 Fujifilm Holdings Corp ハロゲン化銀感光材料およびそれを包含する包装体
EP2068328B1 (fr) 2006-09-28 2014-10-22 FUJIFILM Corporation Écran à émission spontanée et film conducteur transparent
JP5213433B2 (ja) 2006-12-21 2013-06-19 富士フイルム株式会社 導電膜およびその製造方法

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JPS5952817B2 (ja) * 1977-09-06 1984-12-21 富士写真フイルム株式会社 硬調写真画像を形成する方法
JPS56153336A (en) * 1980-04-30 1981-11-27 Fuji Photo Film Co Ltd Formation of photographic image
JPS6035729A (ja) * 1983-08-08 1985-02-23 Fuji Photo Film Co Ltd ハロゲン化銀写真感光材料の処理方法
JPS6190153A (ja) * 1984-10-09 1986-05-08 Fuji Photo Film Co Ltd ハロゲン化銀写真感光材料の処理方法

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