EP0488029B1 - Matériau photographique à l'halogénure d'argent sensible à la lumière - Google Patents

Matériau photographique à l'halogénure d'argent sensible à la lumière Download PDF

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Publication number
EP0488029B1
EP0488029B1 EP91119735A EP91119735A EP0488029B1 EP 0488029 B1 EP0488029 B1 EP 0488029B1 EP 91119735 A EP91119735 A EP 91119735A EP 91119735 A EP91119735 A EP 91119735A EP 0488029 B1 EP0488029 B1 EP 0488029B1
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Prior art keywords
group
silver halide
substituted
emulsion
unsubstituted
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EP0488029A1 (fr
Inventor
Yoichi c/o FUJI PHOTO FILM CO. LTD. Maruyama
Hirotomo C/O Fuji Photo Film Co. Ltd. Sasaki
Yoichi c/o Fuji Photo Film Co. Ltd. Suga
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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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
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/10—Organic substances
    • 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
    • G03C1/09—Noble metals or mercury; Salts or compounds thereof; Sulfur, selenium or tellurium, or compounds thereof, e.g. for chemical sensitising

Definitions

  • the present invention relates to a silver halide photographic light-sensitive material.
  • silver halide emulsions for use in silver halide photographic light-sensitive materials are subjected to chemical sensitization using various chemicals, in order to have desired sensitivities, desired gradation, and the like.
  • chemical sensitizations are: sulfur sensitization, selenium sensitization, noble-metal sensitization such as gold sensitization, reduction sensitization, and any possible combination of these sensitizations.
  • sheets of film for use in printing or X-ray photography are handled directly by hands, and are often bent or folded by hands.
  • Light-sensitive material of any kind receives a high pressure when it is cut or processed.
  • photographic light-sensitive material be provided whose photographic properties are not influenced by the pressure applied to it.
  • a plasticizer such as a polymer or an emulsion compound
  • Another method is to reduce the ratio of the silver halide to the gelatin, both contained in the silver halide emulsion, so as to prevent a pressure from acting on the grains in the emulsion.
  • U.S. Patent 2,960,404 describes the use of polyvalent alcohol;
  • U.S. Patent 3,121,606 discloses the use of carboxyalkyl cellulose.
  • JP-A-49-5017 discloses the use of paraffin and carboxylate.
  • JP-B-53-28086 describes the use of alkylacrylate and organic acid.
  • US-A-4,845,020 discloses a method of processing a silver halide photographic material comprising processing said material in the presence of an organic compound which loses its development restraining function by a reduction oxidation reaction with oxidized developers.
  • the organic compound can be an antifoggant which possesses a moiety according to the Kendall-Pelz rule and either a mercapto group or a cyclic NH group.
  • the compound is one of a number of specific examples of the antifoggant.
  • the object of the present invention is to provide a silver halide photographic light-sensitive material which is high sensitive and has a reduced slight scratch fogging and excels in pressure resistance.
  • the inventors hereof conducted intensive studies on silver halide photographic light-sensitive materials, and successfully made the the silver halide photographic light-sensitive materials, specified below, which fulfill the above-mentioned object.
  • a silver halide photographic light-sensitive material comprises at least one silver halide emulsion layer on a support, wherein silver halide grains contained in the silver halide emulsion layer are chemically sensitized by selenium sensitizer, represented by the following formula (II): where R 1 , R 2 , R 3 , and R 4 each represent alkyl, cycloalkyl, alkenyl, alkynyl, aralkyl, aryl, heterocyclic, acyl, carboxy, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, and sulfamoyl, with the exception of N,N-dimethylselenourea and N,N-diethylselenourea, and the silver halide emulsion layer contains a compound represented by the following formula (I), and/or the oxidized product thereof: formula (I) X 1 - A - X 2 where X 1 and X 2 each represent OR 1 or where
  • EP-A-0 482 599 which is a document according to Article 54(3) EPC, discloses the selenium sensitization of a photographic material by the use of N,N-dimethylselenourea or N,N-diethylselenourea.
  • the selenium sensitizer represented by formula (II) is represented the following formula (III): where R 5 , R 6 , R 7 , and E each represent alkyl, cycloalkyl, alkenyl, alkynyl, aralkyl, aryl, heterocyclic, acyl, carboxy, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, and sulfamoyl, and the E represents a group having Hammett constant ⁇ p of at least -0.1.
  • the silver halide grains are preferably chemically sensitized by at least one of selenium sensitizers represented by the following formula (IV): where R 8 , R 9 , R 10 , and R 11 each represent hydrogen atom, alkyl, cycloalkyl, alkenyl, alkynyl, aralkyl, aryl, heterocyclic, acyl, carboxy, alkoxycarbonyl, aryloxy carbonyl, carbamoyl, and sulfamoyl, and at least one pair of R 8 and R 9 , R 9 and R 10 , R 10 and R 11 , and R 11 and R 8 are bonded to each other, forming a ring.
  • selenium sensitizers represented by the following formula (IV): where R 8 , R 9 , R 10 , and R 11 each represent hydrogen atom, alkyl, cycloalkyl, alkenyl, alkynyl, aralkyl, aryl, heterocyclic,
  • R 1 is a hydrogen atom or a group capable of changing into a hydrogen atom through hydrolysis.
  • R 2 and R 3 are a hydrogen atom, alkyl group, aryl group, heterocylic group, alkylsulfonyl group, arylsulfonyl group, heterocylic carbonyl group, alkylcarbonyl group, arylcarbonyl group, sulfamoyl group, or carbamoyl group.
  • A is substituted or unsubstituted allylene group.
  • the hydrogen atom contained therein is substituted by a group which accelerates the adsorption to a silver halide grain.
  • A is a substituted or unsubstituted allylene group (e.g., phenylene or naphtylene).
  • substituted allylene group are: halogen atom (fluorine, chlorine, bromine), alkyl group (preferably, one having 1 to 20 carbon atoms), aryl group (preferably, one having 6 to 20 carbon atoms), alcoxy group (preferably, one having 1 to 20 carbon atoms), aryloxy group (preferably, one having 6 to 20 carbon atoms), alkylthio group (preferably, one having 1 to 20 carbon atoms), arylthio group (preferably, one having 6 to 20 carbon atoms), acyl group (preferably, one having 2 to 20 carbon atoms), acylamino group (preferably, alkanoylamino group having 1 to 20 carbon atoms or benzoylamino group having 6 to 20 carbon atoms), nitro group, cyano group, oxycarbonyl group (preferably, alkoxycarbonyl group having
  • the compound of formula (I) has two or more substituted groups, these groups can either be identical or different.
  • two substituted groups are ones substituted on adjacent carbon atoms of benzene ring, they are combined, forming 5-, 6- or 7-membered carbon ring or heterocyclic ring which is either saturated or unsaturated.
  • ring-forming compounds examples include: cyclopentane, cyclohexane, cycloheptane, cyclopentene, cyclohexadiene, cycloheptadiene, indan, norbonane, norbornene, benzene, pyridine, and the like. These can have substituting groups.
  • Total carbon atoms in the substituted groups is preferably 1 to 20, more preferably 1 to 10.
  • R 1 which can change into a hydrogen atom through hydrolysis, are - COR 4 (R 4 is alkyl group, either substituted or unsubstituted, aryl group, either substituted or unsubstituted, or anino group, either substituted or unsubstituted), (J is or - SO 2 -, Z is a plurality of atoms required to form at least one 5- or 6-membered heterocyclic ring).
  • R 2 and R 3 are hydrogen atoms, substituted or unsubstituted alkyl group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted alkylsulfonyl sulfonyl group, substituted or unsubstituted group, substituted or unsubstituted heterocyclic sulfonyl group, substituted or unsubstituted alkylcarbonyl group, substituted or unsubstituted arylcarbonyl group, substituted or unsubstituted heterocyclic carbonyl group, substituted or unsubstituted sulfamoyl group, or substituted or unsubstituted carbamoyl group.
  • R 2 and R 3 are hydrogen atoms, substituted or unsubstituted alkyl group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclicsulfonyl group, substituted or unsubstituted heterocycliccarbonyl group, substituted or unsubstituted sulfamoyl group, or substituted or unsubstituted carbamoyl group.
  • R 2 and R 3 can either be identical or different. They can be combined, thus forming nitrogen-containing hetero ring. (For example, they are: morpholino group, pyperrilidino group, pyrrolidino group, or imidazolyl group.)
  • the group accelerating the adsorption to the silver halide is one identified by the following formula: where Y is the group accelerating the adsorption to silver halide, L is a divalent bonding group, m is 0 or 1.
  • Examples of group Y accelerating the adsorption to silver halide are: thioamido group, mercapto group, group having a disulfide bond, and 5- or 6-membered nitrogen-containing heterocyclic group.
  • the heterocyclic group can form a part of a sensitizing dye.
  • the thioamido group represented by Y is a divalent group identified by amino -. It can be a part of a cyclic structure, or noncyclic thioamido group.
  • the thioamido adsorption-accelerating group for use in the present invention can be selected from those which are disclosed in, for example, U.S. Patents 4,030, 925, 4,031,127, 4,080,207, 4,245,037, 4,255,511, 4,266,013, and 4,176,364, Research Disclosure, Vol. 151, No. 15162 (November 1976), and Research Disclosure, Vol. 176, No. 17626 (December 1978).
  • noncyclic thioamido group examples include thioureido group, thiourethane group, and dithiocarbamic ester group.
  • examples of the cyclic thioamido group are 4-thiazoline-2-thione, 4-midazoline-2-thione, 2-thiohydantoine, rhodanine, thiobarbituric acide, tetrazoline-5-thione, 1,2,4-triazoline-3-thione, 1,3,4-thiaziazoline-2-thione, 1,3,4-oxadiazoline-2-thione, benzimidazoline-2-thione, benzyoxazoline-2-thione, and benzothiazoline-2-thione.
  • These cyclic thiamido groups can be further substituted.
  • the mercapto group represented by Y is aliphatic mercapto group, aromatic mercapto group, or heterocyclic mercapto group. (When -SH group is bonded to the carbon atom located adjacent to nitrogen atom, it corresponds to cyclic thioamido group which is a tautomer of the mercapto group. Specific examples of this group are identical to those mentioned above.)
  • the 5- or 6-membered nitrogen-containing heterocyclic group is a 5-membered or 6-membered nitrogen-containing hetero ring consisting of nitrogen, oxygen, sulfur, and carbon atoms. Desirable examples of this group are: benzotriazole, triazole, tetrazole, indazole, benzimidazole, imidazole, benzothiazole, thiazole, benzoxazole, oxazole, thiadiazole, oxadiazole), and triazine, and the like. Any of these group can be substituted by an appropriate substituent group, such as a group of atoms which is required for forming a sensitizing dye.
  • the sensitizing dye can be selected from the dyes disclosed in F.M. Hamer, "Heterocyclic Compounds - Cyanine Dyes and Related Compounds," John Wiley & Cons, Inc., New York, London, 1964.
  • the substituent group can be one described for R 2 , R 3 , or R 4 .
  • a preferable one is cyclicthiamido group (i.e., a mercapto-substituted, nitrogen-containing heterocyclic ring, such as 2-mercaptothiazole, 3-mercapto-1,2,4-triazole, 5-mercaptotetrazole, 2-mercapto-1,3,4-oxadiazole, or 2-mercapto-1,3,4-benzyoxazole), or nitrogen-containing heterocyclic group (e.g., benzotriazole, benzimida zole, or indazole).
  • cyclicthiamido group i.e., a mercapto-substituted, nitrogen-containing heterocyclic ring, such as 2-mercaptothiazole, 3-mercapto-1,2,4-triazole, 5-mercaptotetrazole, 2-mercapto-1,3,4-oxadiazole, or 2-mercapto-1,3,4-benzyoxazole
  • nitrogen-containing heterocyclic group
  • Two or more Y( ⁇ L) ⁇ m groups can substitute; they can either be identical or different.
  • the divalent bonding group can be selected from those identified by the following formulas: -CONH-, -NHCONH-, -SO 2 NH-, -COO-, -NHCOO-, -NHCONHCH 2 CH 2 CONH-, -CH 2 CH 2 SO 2 NH-, -CH 2 CH 2 CONH-
  • the groups, exemplified above, can be substituted by appropriate substituent groups.
  • the substituent groups can be those represented for A .
  • preferable are those represented by the following formula (V): where R 1 , Y, L, and m are identical to those included in formula (I), X 3 is identical to X 1 and X 2 included in formula (I), R 5 is a hydrogen atom or a group which can substitute the hydrogen atom on a benzene ring.
  • the group, which can substitute, is selected from those substituting groups represented for A .
  • R 5 s is either identical or different.
  • X 3 substitutes at an ortho site or a para site of OR 1 .
  • -OR 1 is preferred, and more preferably R 1 is a hydrogen atom.
  • the compound of formula (I) can either contain the oxidized product thereof or consist the oxidized product thereof. It is assumed that most compounds identified by formula (I) contain the oxidized product formed through natural oxidation by air and the like.
  • oxidized product is p-quinones if the compound of formula (I) is hydroquinones, or o-quinone if the compound is catechols.
  • the compound represented by formula (I) is added in an amount of 1 ⁇ 10 -7 mol to 1 ⁇ 10 -2 mol per mol of the silver halide contained in the silver halide photographic light-sensitive material according to the present invention. More preferably, the compound is added in an amount ranging from 1 ⁇ 10 -6 to 5 ⁇ 10 -3 mol per mol of the silver halide.
  • the compound of formula (I) can be added to a hydrophilic colloid solution, preferably to a solution of silver halide emulsion. If the compound is to be added to a silver halide emulsion solution, it can be added at any time prior to the start of chemical sensitization of the silver halide grains, or at any time before the coating of the silver halide emulsion solution.
  • the selenium sensitization is carried out in the method hitherto known. That is, a labile selenium compound and/or an unlabile selenium compound is added to silver halide emulsion. Then, the emulsion is stirred for a predetermined time at high temperature, preferably at 40°C or more. It is desirable that the selenium sensitization disclosed in JP-B-44-15748, wherein use is made of a labile selenium sensitizer, be performed in the present invention.
  • labile selenium sensitizer examples include: aliphatic isoseleno cyanates such as arylisoselenocyanate, selenoureas, selenoketones, selenoamides, selenocarbonic acids and esters, and selenophosphates.
  • aliphatic isoseleno cyanates such as arylisoselenocyanate, selenoureas, selenoketones, selenoamides, selenocarbonic acids and esters, and selenophosphates.
  • aliphatic isoseleno cyanates such as arylisoselenocyanate, selenoureas, selenoketones, selenoamides, selenocarbonic acids and esters, and selenophosphates.
  • the selenium sensitizer represented by the following formula (II) is used as the selenium sensitizer:
  • R 1 , R 2 , R 3 , and R 4 are substituted or unsubstituted alkyl group (e.g., methyl, ethyl, n-propyl, t-butyl, isopropyl, n-octyl), substituted or unsubstituted cycloalkyl group (e.g., cyclopentyl, cyclohexyl, 2-methyl cyclohexyl), substituted or unsubstituted alkenyl group (e.g., aryl, 2-butenyl, 3-pentenyl), substituted or unsubstituted alkynyl group (e.g., propargyl, 3-pentenyl), substituted or unsubstituted aralkyl group (e.g., benzyl group, phenetyl), substituted or unsubstituted aryl group (e.g.,
  • R 1 , R 2 , R 3 , and R 4 which can have substituent groups, are as specificied below:
  • Alkyl group e.g., methyl, ethyl, t-butyl
  • cycloalkyl group e.g., cyclopentyl, cyclohexyl
  • alkenyl group e.g., aryl group, 3-pentenyl
  • alkynyl group e.g., propargyl, 3-pentenyl
  • aralkyl group e.g., benzyl, phenetyl
  • aryl group e.g., phenyl, naphtyl, 4-methylphenyl
  • heterocyclic group e.g., pyridyl, thienyl, furyl, imidazolyl, piperdyl, morphoryl, benzyriazolyl, tetraazaindenyl, indolyl
  • acyl group e.g., acetyl, benzoyl, formyl, pyval
  • R 5 , R 6 , R 7 , and E are alkyl group, cycloalkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group, heterocyclic group, acyl group, carboxy group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, and sulfamoyl group.
  • E is a group having Hammett constant ⁇ p of at least -0.1.
  • R 5 , R 6 , and R 7 are of the same significance as R 1 , R 2 , R 3 , and R 4 included in formula (II).
  • E is a group having Hammett constant ⁇ p of -0.1 or more, preferably 1 or less. (As for the definition of Hammett constant, see Journal of Medicinal Chemistry, Vol. 16, p. 304 (1973), and Vol. 20, p.
  • group E are: substituted or unsubstituted alkyl group (e.g., chloromethyl, trifluoromethyl, acetonyl), substituted or unsubstituted cycloalkyl group (e.g., cyclopentyl), substituted or unsubstituted alkenyl group (e.g., 1-chloro-3-butenyl, 1-chloro-4-octenyl), substituted or unsubstituted alkynyl group (e.g., 1-chloro-3-butynyl, 1-chloro-4-octynyl), substituted or unsubstituted aralkyl group (e.g., benzyl), substituted or unsubstituted aryl group (e.g., phenyl, pentafluorophenyl), substituted or unsubstituted heterocyclic group (e.g., 4-pyridyl, 2-
  • Substituent group of R 5 , R 6 , R 7 , and E are of the same significance as the substituent group of R 1 , R 2 , R 3 , and R 4 included in formula (II).
  • R 5 , R 6 , and R 7 are substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted heterocyclic group, or substituted or unsubstituted acyl group.
  • E also shown in formula (III), is a group having Hammett constant ⁇ p of 0.3 or more.
  • E is substituted or unsubstituted heterocyclic group, substituted or unsubstituted acyl group, substituted or unsubstituted carbamoyl group, substituted alkyl group, or substituted aryl group.
  • R 5 , R 6 , and R 7 are substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, or substituted or unsubstituted acyl group, and E is acyl group having Hammett constant ⁇ p of 0.5 or more.
  • a selenium compound represented by the following formula (IV) can be used as a preferable selenium sensitizer:
  • R 8 , R 9 , R 10 , and R 11 are hydrogen atoms, substituted or unsubstituted alkyl group (e.g., methyl, ethyl, n-propyl, t-butyl, isopropyl, n-octyl), substituted or unsubstituted cycloalkyl group (e.g., cyclopentyl, cyclohexyl, 2-methylcyclohexyl), substituted or unsubstituted alkenyl group (e.g., aryl, 2-butenyl, 3-pentenyl), substituted or unsubstituted alkynyl group (e.g., propargyl, 3-pentynyl), substituted or unsubstituted aralkyl group (e.g., benzyl group, phenetyl), substituted or unsubstituted aryl group (phenyl, naphtyl), substituted
  • Groups which combine with one another, forming a ring, are substituted or unsubstituted alkylene group (including ether group, thioether group, substituted or unsubstituted amino group, such as methylene group, ethylene group, propylene group, butylene group, hexylene group, 1-methylethylene group, -CH 2 CH 2 OCH 2 CH 2 -, -CH 2 CH 2 NHCH 2 CH 2 -), substituted or unsubstituted aralkylene group (e.g., benzylidene), substituted or unsubstituted arylene group (e.g., phenylene, naphtylene), substituted or unsubstituted heterocyclic bonding group (e.g., or bonding group formed by combining these groups (e.g.,
  • Substituent groups for R 8 , R 9 , R 10 , and R 11 can be the same substituent groups described for R 1 , R 2 , R 3 , and R 4 included in formula (II).
  • the ring formed by R 8 and R 9 , the ring formed by R 9 and R 10 , the ring formed by R 10 and R 11 , and the ring formed by R 11 and R 8 are preferably 4- to 8-membered rings.
  • R 8 , R 9 , R 10 , and R 11 are preferably hydrogen atoms, substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted acyl group, and substituted or unsubstituted carbamoyl group.
  • the ring formed by R 8 and R 9 , the ring formed by R 9 and R 10 , the ring formed by R 10 and R 11 , and the ring formed by R 11 and R 8 are more preferably 5- or 6-membered rings, and R 8 , R 9 , R 10 , and R 11 are more preferably hydrogen atoms, substituted or unsubstituted alkyl group, and substituted or unsubstituted acyl group.
  • the compounds identified by formulas (II), (III), and (IV) can be synthesized by the methods known in the art. More specifically, they can be synthesized by the method disclosed in Saul Patai, "The Chemistry of Organic Selenium and Tellurium Compounds," Vol. 2, pp. 255-258 (1987).
  • N-acetyl-N,N',N'-trimethylthiourea (42 g) obtained by method 1-(1) was dissolved in 90 g of methyl iodide, preparing a solution. This solution was stirred for 8 hours at room temperature, thereby obtaining crystal. The crystal was filtered out, and washed with chloroform, thus obtaining 23 g of the target compound.
  • the concentrated solution was extracted with chloroform and water, thereby obtaining a chloroform layer.
  • the chloroform layer was concentrated, dried, and solidified.
  • the resultant crystal was recrystallized with a mixture solvent consisting of 15 ml of ethyl acetate and 10 ml of hexane, whereby 2.3 g of compound II-1 was prepared.
  • the target compound thus prepared, exhibited nuclear magnetic resonance spectrum, mass spectrum, and composition, which coincided with the estimated ones.
  • This compound was synthesized at a yield of 80%, and had a melting point of 87 to 88°C.
  • the target compound, III-29 was obtained in an amount of 2.0 g from 4.0 g of the N,N'-dimethylethylene thiouronium iodide prepared in method 2-(1).
  • the target compound exhibited nuclear magnetic resonance spectrum, mass spectrum, and composition, which coincided with the estimated ones.
  • Compound III-29 was synthesized at a yield of 76%, and had a melting point of 144 to 145°C.
  • the amount of selenium-sensitizer agent used according to the invention depends on its composition, the silver halide grains to be sensitized, the conditions of chemically-ripening the grains, and the like. In most cases, the selenium sensitizer is used in an amount of 10 -8 to 10 -4 mol per mol of silver halide, preferably 10 -7 to 10 -5 mol per mol of silver halide.
  • the conditions, under which to chemically sensitize silver halide grains with the selenium-sensitizing agent of this invention, are not limited in particular. It is desirable, however, that the pAg value be 6 to 11, preferably 7 to 10, an more preferably 7 to 9.5, and that the temperature be 40 to 95°C, preferably 50 to 85°C.
  • the chemical sensitization be performed immediately after silver halide grains have been formed during the manufacture of the emulsion.
  • a noble metal sensitizer such as tellurium, gold, platinum, palladium, iridium
  • gold sensitization should preferably be applied, together with selenium sensitization. More precisely, chloroauric acid, potassium chloroaurate, potassium arurithiocyanate, gold sulfide, gold selenide, and the like can be used as sensitizers, in an amount of 10 -7 to 10 -2 mol per mol of silver halide.
  • sulfur sensitization it is desirable that sulfur sensitization be applied, too.
  • known labile sulfur compounds such as thiosulfates (e.g., hypo), thioureas (e.g., diphenylthiourea, triethylthiourea, arylthiourea), and rhodanines, can be used in an amount of 10 -7 to 10 -2 mol per mol of silver halide.
  • stannous chloride aminoiminomethanesulfonic acid, hydrazine derivaltive, borane derivative, silane compound, polyamine compound, and the like can be used.
  • thiocyanate e.g., potassium thiocyanate
  • thioether compound e.g., the compounds disclosed in U.S. Patents 3,021,215 and 3,271,157, JP-B-58-30571, and JP-A-60-136736, in particular, 3-,6-dithia-1,8-octanediol
  • tetra-substituted thiourea compound e.g., the compounds disclosed in JP-B-59-11892 and U.S.
  • solvents thiocyanate, thioether compound, tetra-substituted thiourea compound, and thione compound are particularly preferable.
  • the solvent is used in an amount of 10 -5 to 5 ⁇ 10 -2 mol per mol of silver halide.
  • the silver halide for use in the present invention is preferably silver bromide, silver iodide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, or silver chloride.
  • the silver halide grains used in the invention are regular crystals such as octohedral ones, or irregular crystals such as spherical ones or tabular ones. Alternatively, a mixture of regular grains and irregular grains can be used. Nonetheless, it is desirable that irregular silver halide grains are used in the present invention.
  • the silver halide grains for use in the invention can consist of either a single homogeneous phase or two different phases, i.e., a core and a shell covering the core.
  • the silver halide grains can be those of, for example, negative-type emulsion, wherein an latent image is formed chiefly on the surfaces of the grains, or those of, for example, inner latent-image type emulsion or pre-fogged direct reverse emulsion, wherein an latent image is formed mainly within the grains.
  • the grains are of the type in which a latent image is formed mainly on their surfaces.
  • the silver halide emulsion for use in the present invention contains tabular grains which have a thickness of 0.5 microns or less, preferably 0.3 microns or less, and a diameter of 0.6 microns or more, and in which those having an average aspect ratio of 5 or more occupy 50% or more of the total projection area.
  • the emulsion can be monodispesant emulsion having a statistical variation coefficient of 20% or less (the variation coefficient being S/d, where S is standard deviation of the projection area in terms of circule-equivalent diameter, and d is the diameter of the grains).
  • use can be made of a mixture of at least one regular-grain emulsion and at least one monodispersant emulsion.
  • the photographic emulsion used in the present invention can be manufactured by various methods. Examples of these methods are disclosed in, for example, P. Glafkides, "Chime et Physique Photographique,” Paul Montel, 1967; G.F. Duffin, “Photographic Emulsion Chemistry,” Focal Press, 1966; V.L. Zelikman et al., “Making and Coating Photographic Emulsion,” Focal Press, 1964.
  • a solvent for silver halide can be used.
  • this solvent are ammonia, potassium rhodanide, antimony rhodanide, thioether compound (e.g., those disclosed in U.S. Patents 3,271,157, 3,574,628, 3,704,130, 4,297,439, and 4,276,374), thion compound (e.g., those disclosed in JP-A-53-144319, JP-A-53-82408, and JP-A55-77737), amine compound (e.g., those disclosed in JP-A-54,100717).
  • the silver halide grains can be grown or physically ripened, in the presence of of cadmium salt, zinc salt, thallium salt, iridium salt or a complex salt thereof, rhodium salt or complex salt thereof, iron salt or complex salt thereof.
  • gelatin be contained, as binder or protective colloid, in the emulsion layers and interlayers of the light-sensitive material according to the present invention.
  • hydrophilic colloid can be used.
  • hydrophilic high-molecular substances are: gelatin derivative; graft polymer formed of gelatin and other high-molecular substance; protein such as albumin and casein; celluose derivative such as hydroxyethyl celluose, carboxymethyl celluose, and cellulose sulfate ester; sugar derivative such as sodium alginate and starch derivative; and monomer or polymer such as polyvinyl alcohol, polyvinylalcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole, and polyvinyl pyrazole.
  • the gelatin for use in the invention can be general-purpose gelatin, gelatin for processing lime stone, acid-processed gelatin, or enzyme-processed gelatin, such those disclosed in Bull. Soc. Sci. Phot. Japan, No. 16, p. 30 (1966). Gelatin subjected to hydrolysis can be used.
  • the light-sensitive material according to the present invention has hydrophilic colloid layers forming photogratic light-sensitive layers or back layers. These colloid layers can contain an inorganic or organic layer-hardening agent. Specific examples of the layer-hardening agent are chromium salt, aldehyde salt (e.g., formaldehyde, glyoxal, glutaraldehyde, N-methylol-series compound (e.g., dimethylol urea).
  • aldehyde salt e.g., formaldehyde, glyoxal, glutaraldehyde
  • N-methylol-series compound e.g., dimethylol urea
  • active halogen compounds e.g., 2,4-dichlor-6-hydroxy-1,3,5-triazine and its soldium salt
  • active vinyl compounds e.g., 1,3-bisvinylsulfonyl-2-propanol, 1,2-bis(vinylsulfonyl acetamide) ethane, bis(vinylsulfonyl methyl) ether, and vinyl-series polymer having vinylsulfonyl group at side chains
  • hydrophilic colloids such as gelatin
  • N-carbamoyl pyridinium salts e.g., (1-morphorlinocarbonyl-3-pyridinio) methanesulfonate
  • haloamidium salts e.g., 1-(1-chloro-1-pyridinomethylene) pyrrolidium 2-naphthalenesulfonate
  • they can harden hydrophilic colloid at high speed, too.
  • the silver halide emulsion for use in this invention can be subjected to spectral sensitization with methin dyes or the like.
  • these dyes are: cyanine dye, merocyanine dye, composite cyanine dye, composite merocyanine dye, holopolar cyanine dye, hemicyanine dye, styryl dye, and hemioxonol dye.
  • the dyes belonging to cyanine dye, merocyanine dye, and composite merocyanine dye are very useful. In these dyes, use can be made of any nucleus usually used in cyanine dye as a basic heterocyclic nucleus.
  • nucleus examples include: a pyrroline nucleus, an oxazoline nucleus, a thiozoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, and a pyridine nucleus.
  • nucleus which has an alicyclic hydrocarbon ring fused to any one of the nuclei named above and a nucleus which has an aromatic hydrocarbon ring fused to any one of the above-mentioned nuclei, such as a indolenine nucleus, a benzindolenine nucleus, an indole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, and a quinoline nucleus.
  • These nuclei can have a substituent group on their carbon atoms.
  • Nuclei having a ketomethylene structure can be used in a merocyanine dye or a composite merocyanine dye.
  • these nuclei are 5- or 6-membered heterocyclic nuclei, such as a pyrazoline-5-one nucleus, a thiohydantoin nucleus, a 2-thioxazolidine-2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanine nucleus, and a thiobarbituric acid nucleus can be used as a nucleus having a ketomethylene structure.
  • the sensitizing dyes can be used singly or in combination.
  • the use of two or more sensitizing dyes, in combination, is desirable, in order to achieve supersensitization.
  • the emulsion can contain, in addition to a sensitizing dye or dyes, a dye incapable of performing spectral sensitization or a substance absorbing virtually no light and capable of performing supersensitization.
  • the dye of this type are aminostylbenzene compound (e.g., those disclosed in, for example, U.S. Patents 2,933,390 and 3,635,721), aromatic organic acid-formaldehyde condensate (e.g., those disclosed in U.S.
  • Patent 3,743,510 cadmium salt, azaindene compound, and the like.
  • the combinations of dyes, which are disclosed in U.S. Patents 3,615,613, 3,615,641, 3,617,295, and 3,635,721 are particularly useful.
  • the silver halide photographic emulsion for use in the present invention can contain various compounds, so that it may not suffer from fogging or its photographic properties may remain stable, during its manufacture or during its storage.
  • examples of such compounds known as antifoggands or stabilizers, are: benzothiazolium salt, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (in particular, 1-phenyl-5-mercaptotetrazole); mercaptopyrizines; mercaptotriazines, thioketo compounds such as oxadolinethione; azaindines (e.g., triazaindine, tetraazaindine (in
  • the light-sensitive material according to the invention can contain a coating aid and one or more surfactants.
  • Surfactants are used for various purposes, for preventing electric charging, for improving sliping property, for dispersing the emulsion, for preventing adhesion, and for improving photographic properties (e.g., development speed, degree of contrast, degree of sensitization).
  • the hydrophilic colloid layers of the light-sensitive material according to the invention can contain a water-soluble dye used as filter dye or for various purposes such as prevention of irradiation or halation.
  • this dye are oxonol dye, hemioxonol dye, styryl dye, merocyanine dye, anthraquinone dye, azo dye.
  • Other dyes, such as cyanine dye, azomethin dye, triarylmethane dye, phthalocyanine dye, are also useful.
  • an oil-suluble dye can be emulsified by means of in-water oil-dispersion method and then be added to the hydrophilic colloid layers.
  • the present invention can be applied to multi-layer color photographic material which comprises a support and at least two emulsion layers formed on the support and having different spectral sensitivities.
  • the multilayer color photographic material of this invention has at least one red-senstive emulsion layer, at least one green-sensitive emulsion layer, and at least one blue-sensitive emulsion layer -- all formed above the support.
  • These emulsion layers can be arranged in any order desired.
  • the red-sensitive layer, the green-sensitive layer, and the blue-sensitive layer are arranged in this order from the side of the support.
  • it is desired that the blue-sensitive layer, the red-sensitive layer, and the green-sensitive layer are arranged in this order from the side of the support.
  • emulsion layers sensitive to the same color can be each formed of two or more layers having different sensitivities, to have an increased sensitivity. Further, three emulsion layers can be combined, thereby forming a layer having an improved graininess. Moreover, a non-light-sensitive layer can be interposed between any two adjacent emulsion layers sensitive to the same color. Still further, an emulsion layer sensitive to a color can be interposed between any adjacent emulsion layers sensitive to another color. Furthermore, a reflection layer containing fine silver halide grains can be provided below a high-sensitive layer, particularly, a layer highly sensitive to blue, thereby to improve the photographic properties of the photographic light-sensitive material.
  • a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer contain a cyan-forming coupler, a magenta-forming coupler, and a yellow-forming coupler, respectively.
  • emulsion layers can be formed in the present invention.
  • infrared-sensitive layers can be combined into a light-sensitive material for use in pseudo-color photography and semiconductor laser-beam exposure.
  • color couplers can be used in the photographic light-sensitive material according to the present invention.
  • Examples of the color couplers are disclosed in the patents set forth in Research Disclosure No. 17643, VII-C to VII-G, and are listed in the following table:
  • a compound which can react with, and can set, formaldehyde described in U.S. Patent 4,411,987 or 4,435,503, is preferably added to the light-sensitive material.
  • the photographic emulsion of this invention be used in color light-sensitive materials.
  • Various color couplers can be used. Specific examples are disclosed in the patents set forth in the above-mentioned Research Disclosure No. 17643, VII-C to VII-G.
  • a yellow coupler Preferred examples of a yellow coupler are described in, e.g., U.S. Patents 3,933,501, 4,022,620, 4,326,024, 4,401,752, and 4,248,961 JP-B-58-10739, British Patents 1,425,020 and 1,476,760, U.S. Patents 3,973,968, 4,314,023, and 4,511,649, and EP 249,473A.
  • magenta coupler examples are preferably 5-pyrazolone and pyrazoloazole compounds, and more preferably, those compounds described in, e.g., U.S. Patents 4,310,619 and 4,351,897, EP 73,636, U.S. Patents 3,061,432 and 3,725,067, Research Disclosure No. 24220 (June 1984), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, JP-A-61-72238, JP-A-60-35730, JP-A-55-118034, and JP-A-60-185951, U.S. Patents 4,500,630, 4,540,654, and 4,556,630, and WO (PCT) 88/04795.
  • Examples of a cyan coupler are phenol and naphthol couplers, and preferably, those described in, e.g., U.S. Patents 4,052,212, 4,146,396, 4,228,233, 4,296,200, 2,369,929, 2,801,171, 2,772,162, 2,895,826, 3,772,002, 3,758,308, 4,334,011, and 4,327,173, EPs 121,365A and 249,453A, U.S. Patents 3,446,622, 4,333,999, 4,775,616, 4,451,559, 4,427,767, 4,690,889, 4,254,212, and 4,296,199, and JP-A-61-42658.
  • a colored coupler for correcting unnecessary absorption of a colored dye are those described in Research Disclosure No. 17643, VII-G, U.S. Patent 4,163,670, JP-B-57-39413, U.S. Patents 4,004,929 and 4,138,258, and British Patent 1,146,368. It is advisable to use a coupler disclosed in U.S. Patent 4,774, 181 which releases a fluorescent dye at the time of coupling, the fluorescent dye correcting unnecessary absorption of a colored dye, or a coupler disclosed in U.S. Patent 4,777,120 which contains, as a releasing group, a dye-precursor group able to react with the developing agent to form a dye.
  • a coupler capable of forming colored dyes having proper diffusibility are those described in U.S. Patent 4,366,237, British Patent 2,125,570, EP 96,570, and West German Patent Application (OLS) No. 3,234,533.
  • Typical examples of polymerized dye-forming couplers are disclosed in, for example, U.S. Patents 3,451,820, 4,080,211, 4,367,288, 4,409,320 and 4,576,910, and British Patent 2,102,137.
  • Couplers releasing a photographically useful residue group on coupling can also be preferably used in the present invention.
  • DIR couplers which releases a development inhibitor are preferably those described in the patents cited in the above-mentioned Research Disclosure No. 17643, VII-F, JP-A-57-151944, JP-A-57-154234, JP-A-60-184248, and JP-A-63-37346, and U.S. Patents 4,248,962 and 4,782,012.
  • Couplers which are particularly preferable for use in the present invention, are such bleaching accelerator releasing couplers as described in JP-B-61-201247 or Research Disclosure No. 11449 (October 1973). These are preferably used in the red-sensitive silver halide emulsion layer located near the support, and can release ⁇ -mercapto propionic acid from the releasing group of phenol-type or, more preferably, naphthol-type coupler residual. These couplers serve to prevent insufficient desilverization which may take place when the light-sensitive material of the invention, containing a tabular-grain emulsion, is subjected to high-speed development.
  • Examples of a coupler which can be used in the light-sensitive material of the present invention are competing couplers described in, for example, U.S. Patent 4,130,427; poly-equivalent coupler disclosed in, for example, U.S. Patents 4,283,427, 4,338,393, and 4,310,618; a DIR redox compound releasing coupler, a DIR coupler releasing coupler, a DIR coupler releasing redox compound, or a DIR redox releasing redox compound, described in, for example, JP-A-60-185950 and JP-A-62-24252; couplers releasing a dye which turns to a colored form after being released, disclosed in EPs 173,302A and 313,308A; bleaching accelerator releasing couplers described in, for example, RD.
  • the color light-sensitive material of the invention contain various antiseptic or antifungal agents, such as 1,2-benzisochinazoline-3-one, n-butyl-p-hydroxybenzoate, phenol, 4-chlor-3, 5-dimethylphenol, 2-phenoxyethanol, 2-(4-thiazolyl) benzoimidazole.
  • various antiseptic or antifungal agents such as 1,2-benzisochinazoline-3-one, n-butyl-p-hydroxybenzoate, phenol, 4-chlor-3, 5-dimethylphenol, 2-phenoxyethanol, 2-(4-thiazolyl) benzoimidazole.
  • the hydrophilic colloid layers in the color photographic light-sensitive material according to the invention preferably have a total thickness of 28 ⁇ m or less, more preferably 23 ⁇ m or less, most preferably 20 ⁇ m or less. It is preferred that the hydrophilic colloid layers has a swelling speed T 1/2 of 30 seconds or less, preferably 20 seconds or less. The thickness of the colloid layers is one measured after these layers had been left to stand for two days at 25°C at relative humidity of 55%.
  • the swelling speed T 1/2 can be measured by the techniques known in the art, by means of, for example, a swellometer of the type which A. Green et al. describe in Photographic Science and Engineering, Vol. 19, No. 2, pp. 124-129.
  • the swelling speed T 1/2 is the period of time which a colloid layer requires to swell to half the saturated thickness, i.e., 90% of the maximum swollen thickness when it is immersed in a color developing liquid at 30°C for 3 minutes and 15 seconds.
  • the swelling speed T 1/2 can be adjusted by adding a proper amount of a hardening agent to gelatin which is used as a binder, or by changing the conditions under which each colloid layer is allowed to age after it has been coated. It is desirable that each hydrophilic colloid layer be swollen to a swelling ratio of 150 to 400%, said swelling ratio calculated as follows: (Tmax - T)/T where T is the thickness of the colloid layer mentioned above, and Tmax is the maximum swollen thickness the layer can have when treated under the above-mentioned conditions.
  • the color photographic light-sensitive materials of the present invention can be developed by the ordinary processes as described, for example, in the above-described Research Disclosure, No. 17643, pages 28 and 29 and ibid., No. 18716, page 651, left to right columns.
  • black-and-white development is carried out, and then color development is effected.
  • black-and-white developer well-known black-and-white developing agents, e.g., a dihydroxybenzene such as hydroquinone, a 3-pyrazolidone such as 1-phenyl-3-pyrazolidone, and an aminophenol such as N-methyl-p-aminophenol can be used singly or in combination.
  • the photographic light-sensitive material of the present invention is normally subjected to washing and/or stabilizing steps after desilvering.
  • the amount of water used in the washing step can be determined over a broad range in accordance with the properties of the light-sensitive material (e.g., a property determined by the substances used such as couplers), the application of the material, the temperature of the washing water, the number of water tanks (the number of stages), a replenishing scheme representing a counter or forward current, and other conditions.
  • the relationship between the amount of water and the number of water tanks in a multi-stage counter-current scheme can be obtained by a method described in "Journal of the Society of Motion Picture and Television Engineers", Vol. 64, PP. 248 - 253 (May, 1955).
  • the amount of water used for washing can be greatly decreased. Since washing water stays in the tanks for a long period of time, however, bacteria multiply and the produced floating substances may be undesirably attached to the light-sensitive material.
  • a method of decreasing calcium and magnesium ions can be effectively utilized, as described in JP-A-62-288838.
  • a germicide such as an isothiazolone compound and cyabendazole described in JP-A-57-8542, a chlorine-based germicide such as chlorinated sodium isocyanurate, and germicides such as benzotriazole described in Hiroshi Horiguchi, "Chemistry of Antibacterial and Antifungal Agents", 1986, published by Sankyo Shuppan, Eiseigijutsu-Kai ed., “Sterilization, Antibacterial, and Antifungal Techniques for Microorganisms", 1982, published by Kogyo Gijutsukai, and Nippon Bokin Bobabi Gakkai ed., “Dictionary of Antibacterial and Antifungal Agents", 1986, can be used.
  • the pH of the water for washing the photographic light-sensitive material of the present invention is 4 to 9, and preferably, 5 to 8.
  • the water temperature and the washing time can vary in accordance with the properties and applications of the light-sensitive material. Normally, the washing time is 20 seconds to 10 minutes at a temperature of 15°C to 45°C, and preferably, 30 seconds to 5 minutes at 25°C to 40°C.
  • the photosensitive material of the present invention can be processed directly by a stabilizer in place of washing. All known methods described in JP-A-57-8543, JP-A-58-14834, and JP-A-60-220345 can be used in such stabilizing process.
  • Stabilization is performed in some cases, after the water-washing, in, for example, a formalin bath which is used as final bath of the color photographic light-sensitive materials.
  • aqueous solution containing 10.5 g of gelatin and 3.0 g of KBr was stirred at 60°C.
  • An aqueous solution of silver nitrate (AgNO 3 , 8.2 g), and an aqueous solution of halides (KBr, 5.7 g; KI, 0.35 g) were added to the aqueous solution thus stirred, over a period of 1 minutes by double jet method. Further, 21.5 g of gelatin was added to the resultant solution, and the solution was heated to 75°C.
  • an aqueous solution of silver nitrate (AgNO 3 , 136.3 g) and an aqueous solution of halides (KBr and 4.2 mol% of KI based on KBr) were added to the heated solution, over a period of 51 minutes by the double jet method, thus accelerating the flow of the additive solutions.
  • the silver potential was maintained at 0 mV with respect to the saturated calomel electrode for first 46 minutes, and was changed to 90 mV thereafter.
  • the solution was cooled to 40°C.
  • an aqueous silver nitrate solution (AgNO 3 , 3.2 g) and a KI aqueous solution (KI, 2.3 g) were added to the cooled solution, over a period of 5 minutes by the double jet method. Further, an aqueous silver nitrate solution (AgNO 3 , 25.4 g) and a KI aqueous solution were added to the solution, over a period of 5.35 minutes by the double jet method, while maintaining the silver potential at -50 mV with respect to the saturated calomel electrode, thereby preparing an emulsion. The emulsion was desalted and added with gelatin.
  • emulsion E contained tabular grains having an average sphere-equivalent diameter of 1.21 ⁇ m, an average thickness of 0.197 ⁇ m, an average aspect ratio of 6.14, and a variation coefficient in circule equivalent diameter of 17%.
  • Emulsion E was subjected gold-sulfur sensitization in the following way. First, emulsion E was heated to 64°C. Next, three sensitizing dyes, Dye-1, Dye-2, and Dye-3, identified by the following formulas, were added to heated emulsion E, in an amount of 4.7 ⁇ 10 -4 mol/mol Ag, in an amount of 1.4 ⁇ 10 -4 mol/mol Ag, and in an amount of 2.0 ⁇ 10 -4 mol/mol Ag, respectively.
  • the antifoggant idenfified by the following formula was added to emulsion E in an amount of 5 ⁇ 10 -5 mol/mol Ag.
  • sodium thiosulfate, chloroaurate, and potassium thiocyanate are sequentially added to the emulsion E in an amount of 8.0 ⁇ 10 -6 mol/mol Ag, an an amount of 1.0 ⁇ 10 -5 mol/mol Ag, and in an amount of 3.0 ⁇ 10 -3 mol/mol Ag.
  • Emulsion E was thereby chemically sensitized appropriately.
  • emulsion E-1 emulsion E-1
  • emulsion E was subjected gold-sulfurselenium sensitization in the following way.
  • emulsion E was heated to 64°C.
  • the sensitizing dyes, Dye-1, Dye-2, and Dye-3 were added to heated emulsion E, in an amount of 4.7 ⁇ 10 -4 mol/mol Ag, in an amount of 1.4 ⁇ 10 -4 mol/mol Ag, and in an amount of 2.0 ⁇ 10 -4 mol/mol Ag, respectively.
  • the above-identified antifoggant was added to emulsion E in an amount of 1 ⁇ 10 -4 mol/mol Ag.
  • sodium thiosulfate, chloroaulate, potassium thiocyanate, and N,N-dimethylselenourea are sequentially added to the emulsion E in an amount of 6.4 ⁇ 10 -6 mol/mol Ag, an an amount of 1.3 ⁇ 10 -5 mol/mol Ag, in an amount of 3.0 ⁇ 10 -3 mol/mol Ag, and in an amount of 1.6 ⁇ 10-6 mol/mol Ag, respectively.
  • Emulsion E was thereby chemically sensitized appropriately, forming emulsion E-2.
  • emulsion E was subjected gold-sulfur-selenium sensitization in the same way as described in the preceding paragraph, except that the below-identified selenium sensitizing agent was used in place of N,N-dimethylselenourea, thereby preparing emulsion E-3.
  • emulsion E was subjected gold-sulfur-selenium sensitization in the same way as in the first-described gold-sulfur-selenium sensitization, except that the below-identified sensitizing agent was used in place of N,N-dimethylselenourea, thereby preparing emulsion E-4.
  • Emulsion E-1 was used in sample 101; emulsion E-2 was used in sample 102; emulsion E-3 was used in sample 103; and emulsion E-4 was used in sample 104.
  • the amounts coated are represented in units of g/m 2 .
  • the amount of silver halide coated is specified in terms of the amount of silver used per square meter.
  • the amounts of sensitizing dyes coated are specified in terms of the number of mols per mol of silver halide used in the same layer.
  • Layer 1 Antihalation Layer Black Colloidal Silver Silver 0.18 Gelatin 1.40
  • Layer 2 Interlayer 2,5-di-t-pentadecylhydroquinone 0.18
  • EX-1 0.070 EX-3 0.020 EX-12 2.0 ⁇ 10 3 U-1 0.060 U-2 0.080 U-3 0.10 HBS-1 0.10 HBS-2 1.020 Gelatin 1.04
  • Layer 3 1st Red-Sensitive Emulsion Layer Emulsion A Silver 0.25 Emulsion B Silver 0.25 Sensitizing Dye-I 6.9 ⁇ 10 -5 Sensitizing Dye-II 1.8 ⁇ 10 -5 Sensitizing Dye-III 3.1 ⁇ 10 -4
  • EX-2 0.34 EX-10 0.020 U-1 0.070 U-2 0.050 U-3 0.070 HBS-1 0.060 Gelatin 0.87
  • Layer 5 3rd Red-Sensitive Emulsion Layer Emulsion D Silver 1.60 Sensitizing Dye-I 5.4 ⁇ 10 -5 Sens
  • All layers mentioned above contained W-1, W-2, W-3, B-4, B-5, F-1, F-2, F-3, F-4, F-5, F-6, F-8, F-9, F-10, F-11, F-12, F-13, iron salt, lead salt, gold salt, platinum salt, iridium salt, and rhodium salt, so that they may have improved storage stability, pressure-resistance, antifungal property, antibacterial property, anti-charging property and coating property.
  • Sample 105 was prepared which was identical to sample 103, except that layer 9 did not contained compound I-9.
  • Sample 106 was prepared which was identical to sample 103, except that the below-identified compound was used in layer 9, in equimolar amount, instead of compound I-9.
  • Sample 107 was prepared which was identical to sample 103, except that compound I-17 shown in Table A was used in layer 9, in equimolar amount, instead of compound I-9.
  • Samples 101 to 107 were left to stand for 14 hours at 40°C at reltive humidity of 70%. Thereafter, they were exposed to white light for 1/100 second, using a wedge. Samples 101 to 107, thus exposed, were developed by the method specified below, and subjected to density measuring. The results were as is shown in Table 2.
  • compositions of the process solutions used were as follows: Color Developing Solution Mother Solution Replenisher Diethylenetriaminepentaacetic acid 1.0 g 1.1 g 1-hydroxyethylidene-1,1-diphosphonic Acid 3.0 g 3.2 g Sodium Sulfite 4.0 g 4.4 g Potassium Carbonate 30.0 g 37.0 g Potassium Bromide 1.4 g 0.7 Potassium Iodide 1.5 mg -- Hydroxylamine Sulfate 2.4 g 2.8 g 4-(N-ethyl-N- ⁇ -hydroxyethylamino)-2-methylalinine Sulfate 4.5 g 5.5 g Water to make 1.0 L 1.0 L pH 10.05 g 10.10 g Fixing Solution Mother Solution Replenisher Sodium Ethylenediaminetetraacetate 0.5 g 0.7 g Sodium sulfite 7.0 g 8.0 g Sodium bisulfite 5.0 g 5.5 g Ammonium Thiosulf
  • Samples 101 to 107 were subjected to pressure-resistance test in the following manner. The samples were left to stand for at least 3 hours in an atmosphere having relative humidity of 55%. Then, in the same atmosphere, a load of 4 g was applied to each sample with a stylus having a diameter of 0.1 mm, and the stylus was moved at speed of 1 cm/sec, thereby scratching the surface of the emulsion layer. Samples 101 to 107 were develop and subjected to density measuring, which was performed by means of an aperture having a diameter of 25 ⁇ m.
  • the silver halide photosensitive materials according to the present invention had high sensitivity and slight scratch fogging (i.e., an increase in fogging density, resulting from scratching). In view of this, the present invention achieved remarkable advantages.

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Claims (3)

  1. Matériau photosensible photographique à l'halogénure d'argent, comprenant au moins une couche d'émulsion d'halogénure d'argent sur un support, dans lequel les grains d'halogénure d'argent contenus dans la couche d'émulsion d'halogénure d'argent sont sensibilisés chimiquement par au moins un sensibilisateur au sélénium représenté par la formule (II) ci-dessous:
    Figure imgb0098
     dans laquelle R1, R2, R3 et R4 représentent chacun un groupe alkyle, cycloalkyle, alcényle, alcynyle, aralkyle, aryle, hétérocyclique, acyle, carboxy, alcoxycarbonyle, aryloxycarbonyle, carbamoyle ou sulfamoyle, à l'exception de la N,N-diméthylsélénourée et de la N,N-diéthylsélénourée, et la couche d'émulsion d'halogénure d'argent contient un composé représenté par la formule (I) ci-dessous et/ou le produit d'oxydation de celui-ci:

            formule (I)    X1 - A - X2

    dans laquelle X1 et X2 représentent chacun OR1 ou
    Figure imgb0099
     dans laquelle R1 représente un atome d'hydrogène ou un groupe capable d'être remplacé par un atome d'hydrogène par hydrolyse, R2 et R3 représentent chacun un atome d'hydrogène, un groupe alkyle, aryle, hétérocyclique, alkylsulfonyle, arylsulfonyle, carbonyle hétérocyclique, alkylcarbonyle, arylcarbonyle, sulfamoyle ou carbamoyle, et A représente un groupe arylène substitué ou non substitué, l'atome d'hydrogène contenu dans au moins l'un parmi X1, X2 et A est substitué par un groupe d'accélération de l'adsorption vis-à-vis d'un grain d'halogénure d'argent.
  2. Matériau photosensible photographique à l'halogénure d'argent selon la revendication 1, caractérisé en ce que le sensibilisateur au sélénium représenté par la formule (II) est représenté par la formule (III) ci-dessous:
    Figure imgb0100
     dans laquelle R5, R6, R7 et E représentent chacun un groupe alkyle, cycloalkyle, alcényle, alcynyle, aralkyle, aryle, hétérocyclique, acyle, carboxy, alcoxycarbonyle, aryloxycarbonyle, carbamoyle ou sulfamoyle, et E représente un groupe présentant une constante de Hammett σp d'au moins-0,1.
  3. Matériau photosensible photographique à l'halogénure d'argent selon la revendication 1, caractérisé en ce que les grains d'halogénure d'argent sont sensibilisés chimiquement par au moins l'un des sensibilisateurs au sélénium représentés par la formule (IV) ci-dessous:
    Figure imgb0101
     dans laquelle R8, R9, R10 et R11 représentent chacun un atome d'hydrogène, un groupe alkyle, cycloalkyle, alcényle, alcynyle, aralkyle, aryle, hétérocyclique, acyle, carboxy, alcoxycarbonyle, aryloxycarbonyle, carbamoyle ou sulfamoyle, et au moins une paire constituée de R8 et R9, R9 et R10, R10 et R11 ou R11 et R8 est réunie pour former un cycle.
EP91119735A 1990-11-19 1991-11-19 Matériau photographique à l'halogénure d'argent sensible à la lumière Expired - Lifetime EP0488029B1 (fr)

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JP2311544A JP2641982B2 (ja) 1990-11-19 1990-11-19 ハロゲン化銀写真感光材料
JP311544/90 1990-11-19

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EP0512496B1 (fr) * 1991-05-10 1995-12-20 Fuji Photo Film Co., Ltd. Matériau photographique à l'halogénure d'argent
DE69328884T2 (de) 1992-03-19 2000-12-07 Fuji Photo Film Co., Ltd. Verfahren zur Herstellung einer photographischen Silberhalogenidemulsion
JPH0675327A (ja) * 1992-08-25 1994-03-18 Fuji Photo Film Co Ltd ハロゲン化銀写真感光材料
US6100020A (en) * 1997-09-19 2000-08-08 Eastman Kodak Company Process for the preparation of silver halide photographic element
DE69811866T2 (de) 1998-06-19 2003-12-24 Ferrania S.P.A., Cairo Montenotte Fotografisches Element mit verbessertem Geschwindigkeit : Dmin Verhältnis und Verfahren zu seiner Herstellung

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EP0482599A1 (fr) * 1990-10-23 1992-04-29 Fuji Photo Film Co., Ltd. Matériau photographique à l'halogénure d'argent sensible à la lumière

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US4565778A (en) * 1983-03-31 1986-01-21 Konishiroku Photo Industry Co., Ltd. Silver halide photographic materials
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
JPS62215272A (ja) * 1986-02-17 1987-09-21 Fuji Photo Film Co Ltd カラ−画像形成方法
JPS62196645A (ja) * 1986-02-24 1987-08-31 Konishiroku Photo Ind Co Ltd 感度・保存性を改良したハロゲン化銀写真感光材料
US4810626A (en) * 1987-02-25 1989-03-07 Eastman Kodak Company Silver halide photosensitive materials containing thiourea and analogue compounds
DE69126815T2 (de) * 1990-04-10 1998-01-29 Fuji Photo Film Co Ltd Photographische Silberhalogenidmaterialien
JP3049335B2 (ja) * 1990-05-21 2000-06-05 富士写真フイルム株式会社 ハロゲン化銀写真感光材料

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EP0482599A1 (fr) * 1990-10-23 1992-04-29 Fuji Photo Film Co., Ltd. Matériau photographique à l'halogénure d'argent sensible à la lumière

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JPH04182637A (ja) 1992-06-30
DE69126405D1 (de) 1997-07-10
EP0488029A1 (fr) 1992-06-03
DE69126405T2 (de) 1997-10-23
JP2641982B2 (ja) 1997-08-20

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