EP0572022A2 - In einer Filmkapsel verpacktes photographischen Material - Google Patents

In einer Filmkapsel verpacktes photographischen Material Download PDF

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Publication number
EP0572022A2
EP0572022A2 EP93108613A EP93108613A EP0572022A2 EP 0572022 A2 EP0572022 A2 EP 0572022A2 EP 93108613 A EP93108613 A EP 93108613A EP 93108613 A EP93108613 A EP 93108613A EP 0572022 A2 EP0572022 A2 EP 0572022A2
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EP
European Patent Office
Prior art keywords
light
encased
silver halide
sensitive material
sensitive
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP93108613A
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English (en)
French (fr)
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EP0572022A3 (de
Inventor
Noboru Sasaki
Mikio Ihama
Toshihiro Nishikawa
Shinzo Kishimoto
Norihiko Sakata
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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Publication date
Priority claimed from JP15896392A external-priority patent/JPH05333480A/ja
Priority claimed from JP16822292A external-priority patent/JPH05341450A/ja
Application filed by Fuji Photo Film Co Ltd filed Critical Fuji Photo Film Co Ltd
Publication of EP0572022A2 publication Critical patent/EP0572022A2/de
Publication of EP0572022A3 publication Critical patent/EP0572022A3/de
Withdrawn legal-status Critical Current

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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
    • G03C3/00—Packages of films for inserting into cameras, e.g. roll-films, film-packs; Wrapping materials for light-sensitive plates, films or papers, e.g. materials characterised by the use of special dyes, printing inks, adhesives
    • 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 an encased photographic material and, more particularly, to an encased photographic material in which the storage stability of a silver halide photographic light-sensitive material encased in a light-transmitting case is improved.
  • Silver halide photographic light-sensitive materials are sensitive to light. Therefore, such materials are generally shielded from light during storage before used in photographing.
  • the light-sensitive material is set in a lightproof container such as a magazine or cartridge, such as a film cartridge of 135-format color negative film.
  • the cartridge containing the light-sensitive material is often encased in a light-transmitting or transparent case.
  • the transparent case allows easy observation of the cartridge encased therein without requiring indications of the type of film on the case, leading to a lower cost. Further, the transparent case can be conveniently reused as a case for keeping small articles.
  • silver halide photographic emulsions for use in silver halide photographic light-sensitive materials are normally subjected to chemical sensitization using various chemical substances in order to obtain, e.g., desired sensitivities and gradations.
  • Representative methods of the chemical sensitization are chalcogen sensitization such as sulfur sensitization or selenium sensitization, noble metal sensitization such as gold sensitization, reduction sensitization, and combinations of these sensitization methods.
  • chalcogen sensitization e.g., the sulfur sensitization or the selenium sensitization is combined with the gold sensitization.
  • the deterioration caused by hydrogen cyanide gas is significant when the grains are sensitized with gold and chalogen.
  • the silver selenide fog centers have a higher fog activity than the silver sulfide fog centers. Because of this, the gold-, (sulfur-) and selenium-sensitized emulsion is more significantly deteriorated than the gold- and sulfur-sensitized emulsion.
  • an encased photographic material comprising: a silver halide light-sensitive material including at least one silver halide emulsion layer on a support, the emulsion layer containing gold- and chalcogen-sensitized silver halide grains and a thiocyanate salt therein; a lightproof container containing the light-sensitive material such that an end portion of the light-sensitive material is positioned outside the lightproof container, and that a gas can pass between an inside and an outside of the lightproof container; a light-transmitting case encasing and sealing the lightproof container; and a hydrogen cyanide gas scavenger present inside the case.
  • the encased photographic material of the invention further comprises a halogen gas scavenger.
  • An encased photographic material of the present invention comprises a silver halide light-sensitive material including at least one silver halide emulsion layer on a support.
  • the emulsion layer contains silver halide grains sensitized with gold and chalcogen, and a thiocyanate salt therein.
  • the light-sensitive material is contained in a lightproof container such that an end portion of the light-sensitive material is positioned outside the lightproof container. Therefore, the end portion of the light-sensitive material is not shielded from light by the lightproof container.
  • a gas can pass between an inside and an outside of the lightproof container.
  • the lightproof container containing the light-sensitive material is encased and sealed in a light-transmitting case.
  • the present invention provides means for eliminating adverse effect of hydrogen cyanide gas generated by light incident upon the unshielded end portion of the light-sensitive material.
  • the generated hydrogen cyanide gas diffuses to the shielded portion of the light-sensitive material and deteriorates the performance of the light-sensitive material.
  • a hydrogen cyanide gas scavenger is present inside the light-transmitting case to capture the generated hydrogen cyanide gas.
  • JP-A-3-505263 discloses that compounds of palladium, gold, and platinum are effective as scavengers for hydrogen cyanide gas. It describes that fog resulting frog hydrogen cyanide gas produced from carbon black can be prevented by adding a hydrogen cyanide gas scavenger to a position at which a light-sensitive emulsion can be protected from the gas. JP-A-3-505263 also describes that the addition position of a scavenger is preferably closer to carbon black, the source of the gas.
  • JP-A-3-505263 has, however, no description indicating that hydrogen cyanide gas is produced when light is radiated onto a light-sensitive material.
  • JP-A-3-505263 therefore, has, of course, no description indicating that hydrogen cyanide gas produced from a portion irradiated with light has an influence on photographic properties of a portion shielded from light.
  • JP-A-3-505263 a thiocyanate salt contained in a light-sensitive material involves the generation of hydrogen cyanide gas.
  • This film is shielded from light by light-shielding black paper containing carbon black in an amount of about 8% (about 0.7 g per a roll of film) with respect to the weight of paper. So it is believed that the film is free from an influence of hydrogen cyanide gas produced upon irradiation with light.
  • a thiocyanate salt causes the generation of hydrogen cyanide gas by the light irradiation on a silver halide.
  • the present invention can also be effectively applied to a photographic material containing a compound which can directly or indirectly generate hydrogen cyanide gas upon light irradiation.
  • the direct or indirect generation of hydrogen cyanide gas means that the mechanism of the generation of hydrogen cyanide gas is complicated, and can not be identified simply. However, the generation of hydrogen cyanide gas can be easily determined. For example, the amount of hydrogen cyanide gas generated can be measured by the following method.
  • Fig. 1 shows a hydrogen cyanide gas trapping device.
  • the trapping device has scrubbing bottles 11, 12, 13 and 14, which are connected with glass tubes 15, 16 and 17 having an inner diameter of 5 mm.
  • Each of the bottles 11, 13 and 14 has an inner volume of 250 cc, and the bottle 12 has an inner volume of one litter.
  • the bottles are available from Shibata Scientific Instrument Industry K.K., Japan.
  • Each of the bottles 11, 13 and 14 contains 100 cc of 1N NaOH, and the bottle contains a sample to be measured.
  • the glass tube 16 is provided with a glass ball 18 having small through pores (G 3) at the end immersed in the liquid in the bottle 13 to improve the trapping efficiency of hydrogen cyanide gas.
  • the glass tube 17 is provided with a glass ball 18 having small through pores (G 3) at the end immersed in the liquid in the bottle 14.
  • An air pump 20 (Iwaki Air Pump (AP-220 ZN)) is connected to the bottle 14 through a glass tube 19.
  • the flow rate of air is adjusted to 700 ⁇ 400 cc/min.
  • the variation of the air flow rate does not largely affect quantitative accuracy of hydrogen cyanide gas.
  • the bottle 11 and 12 are set in a thermostatic chamber at 25°C. When the ambient temperature is within a range of 10 to 30°C, the temperature control of the bottles 13 and 14 is not necessary.
  • a sample of 1 m2 is finely cut and placed in the bottle 12. While light is irradiated on the sample at 10,000 lux for 24 hours, the air pump 20 is operated to trap hydrogen cyanide gas in the bottles 13 and 14.
  • the sample is placed at a relative humidity of about 75%.
  • the air flow rate is controlled to attain a relative humidity of 75 ⁇ 15%, more preferably 75 ⁇ 10%.
  • these layers When light-sensitive layers and back layers of a color photographic light-sensitive material exist, these layers also are preferably adjusted to a pH of 5.5 ⁇ 0.5. If a pH of the light-sensitive layers is 6.0 or less, 90% or more of cyanides generated in the light-sensitive layers by light irradiation volatile as hydrogen cyanide.
  • the amount of hydrogen cyanide gas is 0.1 ⁇ g or more, particularly 0.3 ⁇ g or more, more particularly 0.6 ⁇ g or more.
  • Fog is more readily generated in a color photographic light-sensitive material than in a black-and-white photographic light-sensitive material, and the color photographic light-sensitive material is more damaged than the black-and-white photographic light-sensitive material.
  • An encased photographic light-sensitive material is contained in an outer box having a product name printed thereon.
  • the above-mentioned phenomenon of hydrogen cyanide generation occurs by light transmitted through the box. Therefore, it is possible to suppress the phenomenon by lowering the light transmissivity of the box.
  • the box it is, however, necessary for the box to be printed with an ink having a large light absorptivity, i.e., a dark ink. This is not practical since the box must be so designed as to attract attention.
  • the box is constructed of a composite material of paper and light-shielding material, the problem can be solved. However, the use of such a composite material increases the cost of the photographic product.
  • the present invention provides an effective method for without increasing the cost of the product.
  • a hydrogen cyanide gas scavenger according to the present invention is a compound that converts hydrogen cyanide gas, produced when a light-sensitive material is irradiated with light, into a photographically inert substance.
  • the hydrogen cyanide gas scavenger of the present invention has no chemical sensitization effect.
  • the scavenger should not release any substance having an adverse effect on silver halide light-sensitive materials, as a result of trapping of hydrogen cyanide gas.
  • An appropriate hydrogen cyanide gas scavenger can be selected from inorganic or organic compounds of noble metals. Most preferred are compounds of palladium (II or IV) and platinum (II or IV).
  • a compound of gold (I or III) is also preferable.
  • compounds of rhodium (III), iridium (III or IV), and osmium (II, III, or IV) are also effective, a larger amount is required to obtain an equivalent effect when these compounds are used.
  • platinum compounds are platinum(II) chloride, platinum(IV) chloride, hexafluoroplatinate(IV), tetrachloroplatinate(II), hexachloroplatinate(IV), trichlorotrifluoroplatinate(IV), tetrabromoplatinate(II), hexabromoplatinate(IV), dibromodichloroplatinate(II), hexahydroxoplatinate(IV), bis(oxalato)platinate(II), dichlorobis(oxalato)platinate(IV), bis(thiooxalato)platinate(II), bis(acetylacetonato)platinum(II), bis(1,1,1,5,5,5-hexafluoro-2,4-pentanedionato)platinum(II), bis(1,1,1-trifluoro-2,4-pentanedionato)platinum(II),
  • Examples of compounds of gold(I or III), rhodium(III), iridium(III or IV), and osmium(II, III, or IV) are potassium tetrachloroaurate(III), rhodium(III) chloride, potassium hexachloroiridate(IV), potassium tetrachloroiridate(III), and potassium hexachloroosmate(IV).
  • Inorganic or organic compounds of noble metals are not limited to the above examples as long as the effect of the present invention can be obtained.
  • the hydrogen cyanide gas scavenger can be present at any position inside the sealed case; the hydrogen cyanide gas scavenger can be coated on or incorporated in the inner surface of the sealed case or coated on or incorporated in a part forming a cartridge.
  • the hydrogen cyanide gas scavenger is present in a photographic light-sensitive material.
  • a photographic light-sensitive material is normally constituted by a support, a back layer, emulsion layers, surface protective layers, interlayers, and an antihalation layer.
  • the hydrogen cyanide gas scavenger of the present invention is added directly to these layers and coated in the form of layers, or coated separately together with an appropriate solvent or binder.
  • a water-soluble scavenger can be added in the form of an aqueous solution with a proper concentration.
  • a scavenger which is insoluble or sparingly soluble in water can be dissolved in an appropriate organic solvent, such as alcohols, glycols, ketone, esters, or amides, that is miscible with water and has no adverse effect on photographic properties, and added in the form of a solution.
  • a back layer, emulsion layers, a surface protective layer, interlayers, and an antihalation layer are generally dispersions using binders.
  • useful binders are a naturally produced polymeric vehicle, such as gelatin and a cellulose derivative, and a synthetic vehicle, such as polyvinyl alcohol and its derivative, acrylate and methacrylate polymers, and a butadiene-styrene polymer and a similar substance.
  • the hydrogen cyanide gas scavenger is to be added directly to these layers, the conditions, such as the concentration and the pH of a binder must be selected carefully in accordance with the type and the amount of the hydrogen cyanide gas scavenger to be used.
  • a noble metal compound and gelatin interact, and this sometimes significantly raises the viscosity of the system depending on the conditions.
  • palladium(II) ions and gelatin is described in detail in Journal of Japan Photographic Society, Vol. 34, page 159 (1971), Keiichi Tanaka; Journal of Japan Photographic Society, Vol. 37, page 133 (1974), Keiichi Tanaka; Journal of Japan Photographic Society, Vol. 39, page 73 (1976), Keiichi Tanaka; Journal of Photographic Science, Vol. 21, page 134 (1973), Keiichi Tanaka; and Journal of Photographic Science, Vol. 26, page 222 (1978), Keiichi Tanaka.
  • Palladium(II) ions strongly bond with amide linkage and amino acid residues of gelatin, and hence sometimes form a bulk foreign matter of gelatin depending on the conditions. Therefore, it is preferable to select a proper palladium compound described above in accordance with the conditions.
  • the addition amount of the hydrogen cyanide gas scavenger must be so determined as to fall within a range over which the effect of the present invention can be obtained significantly.
  • the addition amount is preferably 1/10 mol or more, more preferably 1/2 to 100 mol, and most preferably 1 to 10 mol per mol of thiocyanate contained in that portion of a silver halide light-sensitive material which may be irradiated with light during storage or before photographing.
  • a halogen gas scavenger is also effective in eliminating the adverse effect of hydrogen cyanide produced light irradiation upon the light-sensitive material before photographing of the material.
  • the halogen gas scavenger of the invention is a compound that converts halogen gas, produced when a light-sensitive material is irradiated with light, into a photographically inert substance.
  • the scavenger therefore, should not release any substance having an adverse effect on silver halide light-sensitive materials, as a result of trapping of halogen gas.
  • halogen gas scavenger It is generally known that gelatin acts as a halogen gas scavenger and its actions are the functions of the pH and the pAg of the system. In the present invention, however, it is preferable to use a compound given below be present as a halogen gas scavenger at a position inside the sealed case encasing the light-sensitive material.
  • Preferred halogen scavengers are sulfide compounds, nitrite salts, semicarbazides, sulfite salts, hydroquinones, ethylenediamine, acetonesemicarbazone, and p-hydroxyphenylglycine.
  • Particulary preferred halogen gas scavengers are those represented by Formula (H) below:
  • each of R1, R2, R3, and R4 represents a hydrogen atom or a group substitutable on the benzene nucleus.
  • halogen atom e.g., a fluorine atom, a chlorine atom, and a bromine atom
  • an alkyl group most preferably one having 1 to 32 carbon atoms, e.g., methyl, ethyl, n-propyl, t-butyl, n-amyl, i-amyl, n-octyl, n-dodecyl, and n-octadecyl
  • an alkenyl group e.g., an aryl group, an acyl group, a cycloalkyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylacylamino group, an arylacylamino group, an alkylcarbamoyl group, an arylcarbamoyl group, an alkylcarbonamido group,
  • the halogen gas scavenger of the present invention may be present either in a non-light-sensitive layer, such as a protective layer, an interlayer, or a back layer formed on a surface of film opposite to the emulsion surface, or a silver halide emulsion layer.
  • a non-light-sensitive layer such as a protective layer, an interlayer, or a back layer formed on a surface of film opposite to the emulsion surface, or a silver halide emulsion layer.
  • the halogen gas scavenger is more preferably added to a layer formed on the emulsion layer side of a support and farther from the support.
  • the addition amount of the halogen gas scavenger is preferably 0.05 to 1 g/m2, and more preferably 0.1 to 0.5 g/m2.
  • a compound which can directly or indirectly generate hydrogen cyanide gas upon light irradiation on the light-sensitive material includes an inorganic compound such as a selenocyanate salt, a cyano complex salt or a selenocyano complex salt, and an organic compound having a cyano group.
  • the silver halide photographic light sensitive material in the present invention has a silver halide emulsion layer on a support.
  • the support is described in Research Disclosure (RD) No. 17643, page 28, RD No. 18716, page 647, right column to page 648, left column and RD No. 307105, page 879.
  • the silver halide emulsion used in the present invention is subjected to gold sensitization and chalcogen sensitization.
  • the chalcogen sensitization is performed by using at least one of selenium, sulfur, and tellurium sensitizers.
  • the gold-chalcogen sensitization is selected from gold-sulfur, gold-selenium, gold-tellurium, gold-surfur-selenium, gold-sulfur-tellurium, gold-selenium-tellurium, and gold-sulfur-selenium-tellurium sensitizations.
  • the selenium sensitization is performed by conventionally known methods. That is, the selenium sensitization is normally performed by adding a labile selenium compound and/or a non-labile selenium compound to an emulsion and stirring the emulsion at a high temperature, preferably 40°C or more for a predetermined period of time. Selenium sensitization using the labile selenium compounds described in JP-B-44-15748 ("JP-B" means Published Examined Japanese Patent Application) is preferably performed.
  • labile selenium sensitizer examples include aliphatic isoselenocyanates, such as allylisoselenocyanate, selenoureas, selenoketones, selenoamides, selenocarboxylic acids and selenocarboxylate esters, and selenophosphates.
  • Most preferable labile selenium compounds are as follows.
  • Organic selenium compound in which a selenium atom is double-bonded to a carbon atom of an organic compound by a covalent bond
  • labile selenium compound used as a sensitizer for a photographic emulsion is not so important as long as selenium is labile, and that the organic part of the molecule of the selenium sensitizer has no important role except the role of carrying selenium and keeping it in a labile state in an emulsion. In the present invention, therefore, labile selenium compounds in this broad concept are advantageously used.
  • Non-labile selenium compounds include selenious acid, potassium selenocyanide, selenazoles, quaternary ammonium salts of selenazoles, diarylselenide, diaryldiselenide, 2-selenazolidinedione, 2-selenoxazolidinethione, and derivatives of these compounds.
  • Non-labile selenium sensitizers and thioselenazolidinedione compounds described in JP-B-52-38408 are also useful.
  • Z1 and Z2 may be the same or different and each represents an alkyl group (e.g., methyl, ethyl, t-butyl, adamantyl, and t-octyl), an alkenyl group (e.g., vinyl and propenyl), an aralkyl group (e.g., benzyl and phenethyl), an aryl group (e.g., phenyl, pentafluorophenyl, 4-chlorophenyl, 3-nitrophenyl, 4-octylsulfamoylphenyl, and ⁇ -naphthyl), a heterocyclic group (e.g., pyridyl, thienyl, furyl, and imidazolyl), -NR1(R2), -OR3, or -SR4.
  • alkyl group e.g., methyl, ethyl, t-butyl, adam
  • R1, R2, R3, and R4 may be the same or different and each represents an alkyl group, an aralkyl group, an aryl group, or a heterocyclic group.
  • Examples of the alkyl group, the aralkyl group, the aryl group, and the heterocyclic group can be the same as those enumerated above for Z1.
  • each of R1 and R2 can be a hydrogen atom or an acyl group (e.g., acetyl, propanoyl, benzoyl, heptafluorobutanoyl, difluoroacetyl, 4-nitrobenzoyl, ⁇ -naphthoyl, and 4-trifluoromethylbenzoyl).
  • Z1 preferably represents an alkyl group, an aryl group, or -NR1(R2) and Z2 preferably represents -NR5(R6) wherein R1, R2, R5, and R6 may be the same or different and each represents a hydrogen atom, an alkyl group, an aryl group, or an acyl group.
  • a selenium compound represented by Formula (I) are N,N-dialkylselenourea, N,N,N'-trialkyl-N'-acylselenourea, tetraalkylselenourea, N,N-dialkyl-arylselenoamide, and N-alkyl-N-aryl-arylselenoamide.
  • Z3, Z4, and Z5 may be the same or different and each represents an aliphatic group, an aromatic group, a heterocyclic group, -OR7, -NR8(R9), -SR10, -SeR11, X, or a hydrogen atom.
  • Each of R7, R10, and R11 represents an aliphatic group, an aromatic group, a heterocyclic group, a hydrogen atom, or a cation
  • each of R8 and R9 represents an aliphatic group, an aromatic group, a heterocyclic group, or a hydrogen atom
  • X represents a halogen atom.
  • an aliphatic group represented by Z3, Z4, Z5, R7, R8, R9, R10, or R11 represents a straight-chain, branched, or cyclic alkyl, alkenyl, alkynyl, or aralkyl group (e.g., methyl, ethyl, n-propyl, isopropyl, t-butyl, n-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopentyl, cyclohexyl, allyl, 2-butenyl, 3-pentenyl, propargyl, 3-pentynyl, benzyl, and phenethyl).
  • aralkyl group e.g., methyl, ethyl, n-propyl, isopropyl, t-butyl, n-butyl, n-octyl, n-
  • an aromatic group represented by Z3, Z4, Z5, R7, R8, R9, R10, or R11 represents a monocyclic or condensed-ring aryl group (e.g., phenyl, pentafluorophenyl, 4-chlorophenyl, 3-sulfophenyl, ⁇ -naphthyl, and 4-methylphenyl).
  • a heterocyclic group represented by Z3, Z4, Z5, R7, R8, R9, R10, or R11 represents a 3-to 10-membered saturated or unsaturated heterocyclic group (e.g., pyridyl, thienyl, furyl, thiazolyl, imidazolyl, and benzimidazolyl) containing at least one heteroatom selected from a nitrogen atom, an oxygen atom, and a sulfur atom.
  • a cation represented by R7, R10, or R11 represents an alkali metal atom or ammonium
  • a halogen atom represented by X represents a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.
  • Z3, Z4, or Z5 preferably represents an aliphatic group, an aromatic group, or -OR7, and R7 preferably represents an aliphatic group or an aromatic group.
  • More preferable examples of a compound represented by Formula (II) are trialkylphosphineselenide, triarylphosphineselenide, trialkylselenophosphate, and triarylselenophosphate.
  • selenium sensitizers are added in the form of a solution by dissolving in water, an organic solvent, such as methanol or ethanol, or a solvent mixture of these solvents, or in the form described in JP-A-4-140738 or JP-A-4-140739, so that they may be present during chemical sensitization.
  • the selenium sensitizers are preferably added before start of chemical sensitization.
  • a selenium sensitizer to be used is not limited to one type, but two or more of the selenium sensitizers described above can be used together.
  • a combination of the labile selenium compound and the non-labile selenium compound may be used.
  • the addition amount of the selenium sensitizer used in the present invention varies depending on the activity of each selenium sensitizer used, the type or grain size of a silver halide, and the temperature and time of ripening.
  • the addition amount is preferably 1 ⁇ 10 ⁇ 8 mole or more, and more preferably 1 ⁇ 10 ⁇ 7 to 1 ⁇ 10 ⁇ 4 mole per mole of silver halide.
  • the temperature of chemical ripening is preferably 45°C or more, and more preferably 50°C to 80°C.
  • the pAg and the pH can be set as desired. For example, the effect of the present invention can be obtained by a pH over a wide range of 4 to 9.
  • the selenium sensitization can be performed more effectively in the presence of a silver halide solvent.
  • Examples of the silver halide solvent usable in the present invention are (a) organic thioethers described in U.S. Patents 3,271,157, 3,531,289, and 3,574,628, JP-A-54-1019 ("JP-A" means Published Unexamined Japanese Patent Application), and JP-A-54-158917, (b) thiourea derivatives described in JP-A-53-82408, JP-A-55-77737, and JP-A-55-2982, (c) silver halide solvents having a thiocarbonyl group sandwiched between an oxygen or sulfur atom and a nitrogen atom, described in JP-A-53-144319, (d) imidazoles described in JP-A-54-100717, (e) sulfite salts, and (f) thiocyanates. Most preferable silver halide solvents are thiocyanate and tetramethylthiourea.
  • a preferable amount of, e.g., thiocyanate is 1 ⁇ 10 ⁇ 4 to 1 ⁇ 10 ⁇ 2 mol per mol of silver halide.
  • the sulfur sensitization is normally performed by adding a sulfur sensitizer to an emulsion and stirring the emulsion at a high temperature, preferably 40°C or more for a predetermined time.
  • the gold sensitization is normally performed by adding a gold sensitizer to an emulsion and stirring the emulsion at a high temperature, preferably 40°C or more for a predetermined time.
  • Sulfur sensitizers known to those skilled in the art can be used in the sulfur sensitization.
  • the sulfur sensitizer are thiosulfate salts, allylthiocarbamidothioureas, allylisothiacyanate, cystine, p-toluenethiosulfonate salts, and rhodanine.
  • the sulfur sensitizer is used in an amount sufficient to effectively increase the sensitivity of an emulsion. Although this amount varies over a wide range depending on various conditions such as the pH, the temperature, and the size of silver halide grains, it is preferably 1 ⁇ 10 ⁇ 7 to 1 ⁇ 10 ⁇ 4 mol per mol of silver halide.
  • the gold sensitizer for use in the gold sensitization of the present invention can be any gold compound having an oxidation number of gold of +1 or +3, and it is possible to use gold compounds normally used as gold sensitizers.
  • Representative examples of the gold sensitizer are chloroaurate, potassium chloroaurate, auric trichloride, potassium auricthiocyanate, potassium iodoaurate, tetracyanoauric acid, ammonium aurothiacyanate, and pyridyltrichlorogold.
  • the addition amount of the gold sensitizers varies depending on various conditions, it is preferably 1 ⁇ 10 ⁇ 7 and 1 ⁇ 10 ⁇ 4 mol per mol of silver halide.
  • the thiocyanate salt is used in any of these gold-chalcogen sensitizations.
  • Preferable examples of the thiocyanate salt are an ammonium salt, a potassium salt, and a sodium salt.
  • the thiocyanate salt can be added either singly or in the form of a mixture with gold sensitizers in the gold-chalcogen sensitization.
  • the thiocyanate salt can be added either in portions or continuously.
  • the thiocyanate salt is more preferably used not only in the gold-chalcogen sensitization, but in grain formation or desalting.
  • the use of a thiocyanate salt during grain formation is described in U.S. Patents 3,320,069 and 4,434,226.
  • a silver halide light-sensitive material of the present invention has an ISO sensitivity of preferably 100 to 3,200, and more preferably 400 to 3,200.
  • a photographic light-sensitive material is contained in a lightproof container such that an end portion of the light-sensitive material is located at a position at which it may be irradiated with light (outside the container) and the remaining portion is located at a position at which it is shielded from light (within the container). Air circulates through the portion to be irradiated with light and the portion to be shielded therefrom.
  • the light-sensitive material contained in the lightproof container is encased in a light-transmitting case.
  • the lightproof container of the present invention includes a cassette for sheet film, it is typically a cartridge for roll film.
  • the cartridge for roll film has a spool around which a silver halide light-sensitive material is wound into the form of a roll, a film slit through which the light-sensitive material is inserted and extracted, and a cartridge main body for housing the spool such that the spool is rotatable around the axis.
  • the spool has a flange for shielding light: the flange prevents external light from entering the cartridge through a gap formed between a cap, which is arranged on one end portion of the cartridge main body, typically a cylindrical body portion, and the spool. It is also preferable to provide a light-shielding member at the film slit to allow smooth extraction and rewind of film. This light-shielding member is described in Published Examined Japanese Utility Model Application No. 61-34526.
  • a currently widely distributed 135-format roll film corresponds to a photographic material of this type. That is, as shown in Fig. 2, a silver halide photographic light-sensitive material 24 is contained in a metal cartridge 22 having a plastic spool 21 as its shaft and is in part extracted from a film extraction portion 23 via a light-shielding ribbon. For convenience of film loading, several centimeters of film are normally extracted, and this portion 25 corresponds to the position which may be irradiated with light before photographing. Air circulates from the portion 25 to a portion to be shielded from light through the film extraction portion 23 or a gap formed in the cartridge 22.
  • the cartridge 22 containing the silver halide photographic light-sensitive material 24 is encased and sealed in a cartridge case 26 and a cap 27.
  • the sealed case 26 is so designed as to shield gas that is harmful to light-sensitive materials and suppress permeation of excess water vapor.
  • the permeabilities to gas and water vapor largely depend on the structures and the materials of the cartridge case 26 and the cap 27.
  • the humidity inside the sealed case 26 is preferably maintained constant.
  • a relative humidity inside the sealed case at 25°C is preferably 55% or more, more preferably 55% to 70%, and most preferably 55% to 65%.
  • the humidity inside the sealed case is maintained constant means that when the difference in humidity between the atmosphere and the interior of the case is 20%, a change in humidity inside the case is 10% or less when the case is left to stand at 25°C for 12 months.
  • the equilibrium humidity in the present invention is a value measured at 25°C and can be measured by conventional methods (the equilibrium humidity can be measured by a capacitance humidity measurement device, such as a HUMICAP humidity sensor available from VAISALA K.K.)
  • the cartridge case 26 and/or the cap 27 is light-transmitting, i.e., transparent or semitransparent.
  • Transparent or semitransparent means that the portion 25 extracted from the film extraction portion 23 may be exposed essentially to external light before photographing. More specifically, when the film is left to stand under radiation of light of 10,000 lux for 24 hours, an increase in fog in the portion 25 extracted from the film extraction portion 23 is 0.1 or more, preferably 0.3 or more, and more preferably 0.5 or more, or overall fog is caused.
  • Plastic materials for forming the transmitting case 26 or cap 27 can be manufactured by addition polymerization of an olefin having a carbon-carbon double bond, ring-opening polymerization of a small number-membered cyclic compound, polycondensation (condensation polymerization) of two or more types of polyfunctional compounds, polyaddition, or addition condensation of a phenol derivative, a urea derivative or a melamine derivative with a compound having an aldehyde.
  • olefin having a carbon-carbon double bond as the raw material for forming the plastic material of the present invention, are styrene, ⁇ -methylstyrene, butadiene, methyl methacrylate, butyl acrylate, acrylonitrile, vinyl chloride, vinylidene chloride, vinylpyridine, N-vinylcarbazole, N-vinylpyrrolidone, vinylidene cyanide, ethylene, and propylene.
  • small number-membered cyclic compound examples include ethylene oxide, propylene oxide, glycidol, 3,3-bischloromethyloxetane, 1,4-dioxane, tetrahydrofuran, trioxane, ⁇ -caprolactam, ⁇ -propiolactone, ethyleneimine, and tetramethylsiloxane.
  • polyfunctional compound examples include carboxylic acids, such as terephthalic acid, adipic acid, and glutaric acid; isocyanates, such as toluenediisocyanate, tetramethylenediisocyanate, and hexamethylenediisocyanate; alcohols, such as ethyleneglycol, propyleneglycol, and glycerin; amines, such as hexamethylenediamine, tetramethylenediamine, and paraphenylenediamine; and epoxy.
  • carboxylic acids such as terephthalic acid, adipic acid, and glutaric acid
  • isocyanates such as toluenediisocyanate, tetramethylenediisocyanate, and hexamethylenediisocyanate
  • alcohols such as ethyleneglycol, propyleneglycol, and glycerin
  • amines such as hexamethylenediamine, tetramethylenediamine, and para
  • Representative examples of the compound having an aldehyde are formaldehyde, acetaldehyde, octanal, dodecanal, and benzaldehyde. Two or more types of these raw materials can be used together in accordance with the target performance.
  • a catalyst or a solvent is sometimes used in the manufacture of the plastic material using these raw materials.
  • the catalyst examples include a free-radical polymerization catalyst, such as (1-phenylethyl)azodiphenylmethane, dimethyl-2,2'-azobisisobutylate, 2,2 ⁇ -azobis(2-methylpropane), benzoylperoxide, cyclohexanone peroxide, and potassium persulfate; a cation polymerization catalyst, such as sulfuric acid, toluenesulfonic acid, trifluorosulfuric acid, perchloric acid, trifluoroboric acid, and tin tetrachloride; an anion polymerisation catalyst, such as n-butyllithium, sodium/naphthalene, 9-fluorenyllithium, and phenylmagnesium bromide; a triethylaluminum/tetrachlorotitanium-based Ziegler-Natta catalyst; sodium hydroxide; potassium hydroxide; and a potassium metal.
  • the solvent is not particularly limited as long as it does not inhibit polymerization. Examples are hexane, decalin, benzene, toluene, cyclohexane, chloroform, acetone, methylethylketone, ethyl acetate, butyl acetate, and tetrahydrofuran.
  • plasticizer In molding of plastic material, a plasticizer is mixed in plastic material as needed.
  • Representative examples of the plasticizer are trioctylphosphate, tributylphosphate, dibutylphthalate, diethylsebacate, methylamylketone, nitrobenzene, ⁇ -valerolactone, di-n-octylsuccinate, bromonaphthalene, and butylpalmitate.
  • the light-sensitive material in the present invention needs only to have at least one of silver halide emulsion layers, i.e., a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer, formed on a support.
  • the number or order of the silver halide emulsion layers and the non-light-sensitive layers are particularly not limited.
  • a typical example is a silver halide photographic light-sensitive material having, on a support, at least one unit light-sensitive layer constituted by a plurality of silver halide emulsion layers which are sensitive to essentially the same color but have different sensitivities or speeds.
  • the unit light-sensitive layer is sensitive to blue, green or red light.
  • the unit light-sensitive layers are generally arranged such that red-, green-, and blue-sensitive layers are formed from a support side in the order named. However, this order may be reversed or a layer having a different color sensitivity may be sandwiched between layers having the same color sensitivity in accordance with the application.
  • Non-light-sensitive layers such as various types of interlayers may be formed between the silver halide light-sensitive layers and as the uppermost layer and the lowermost layer.
  • the interlayer may contain, e.g., couplers and DIR compounds as described in JP-A-61-43748, JP-A-59-113438, JP-A-59-113440, JP-A-61-20037, and JP-A-61-20038 or a color mixing inhibitor which is normally used.
  • a two-layered structure of high- and low-speed emulsion layers can be preferably used as described in West German Patent 1,121,470 or British Patent 923,045.
  • layers are preferably arranged such that the sensitivity or speed is sequentially decreased toward a support, and a non-light-sensitive layer may be formed between the silver halide emulsion layers.
  • layers may be arranged such that a low-speed emulsion layer is formed remotely from a support and a high-speed layer is formed close to the support.
  • layers may be arranged from the farthest side from a support in an order of low-speed blue-sensitive layer (BL)/high-speed blue-sensitive layer (BH)/high-speed green-sensitive layer (GH)/low-speed green-sensitive layer (GL)/high-speed red-sensitive layer (RH)/low-speed red-sensitive layer (RL), an order of BH/BL/GL/GH/ RH/RL, or an order of BH/BL/GH/GL/RL/RH.
  • BL low-speed blue-sensitive layer
  • BH high-speed blue-sensitive layer
  • GH high-speed green-sensitive layer
  • GL high-speed red-sensitive layer
  • RH red-sensitive layer
  • RL low-speed red-sensitive layer
  • layers may be arranged from the farthest side from a support in an order of blue-sensitive layer/GH/RH/GL/RL.
  • layers may be arranged from the farthest side from a support in an order of blue-sensitive layer/GL/RL/GH/RH.
  • three layers may be arranged such that a silver halide emulsion layer having the highest sensitivity is arranged as an upper layer, a silver halide emulsion layer having sensitivity lower than that of the upper layer is arranged as an intermediate layer, and a silver halide emulsion layer having sensitivity lower than that of the intermediate layer is arranged as a lower layer.
  • three layers having different sensitivities may be arranged such that the sensitivity is sequentially decreased toward the support.
  • these layers may be arranged in an order of medium-speed emulsion layer/high-speed emulsion layer/low-speed emulsion layer from the farthest side from a support in a layer having the same color sensitivity as described in JP-A-59-202464.
  • an order of high-speed emulsion layer/low-speed emulsion layer/medium-speed emulsion layer, or low-speed emulsion layer/medium-speed emulsion layer/high-speed emulsion layer may be adopted. Furthermore, the arrangement can be changed as described above even when four or more layers are formed.
  • a donor layer (CL) of an interlayer effect can be arranged directly adjacent to, or close to, a main light-sensitive layer such as BL, GL or RL.
  • the donor layer has a spectral sensitivity distribution which is different from that of the main light-sensitive layer.
  • Donor layers of this type are disclosed in U.S. Patent 4,663,271, U.S. Patent 4,705,744, U.S. Patent 4,707,436, JP-A-62-160448, and JP-A-63-89850.
  • a preferable silver halide contained in photographic emulsion layers of the photographic light-sensitive material of the present invention is silver bromoiodide, silver chloroiodide, or silver chlorobromoiodide containing about 30 mol% or less of silver iodide.
  • the most preferable silver halide is silver bromoiodide or silver chlorobromoiodide containing about 2 mol% to about 10 mol% of silver iodide.
  • Silver halide grains contained in the photographic emulsion may have regular crystals such as cubic, octahedral, or tetradecahedral crystals, irregular crystals such as spherical, or tabular crystals, crystals having defects such as twin planes, or composite shapes thereof.
  • the silver halide may consist of fine grains having a grain size of about 0.2 ⁇ m or less or large grains having a projected-area diameter of up to 10 ⁇ m, and the emulsion may be either a polydisperse emulsion or a monodisperse emulsion.
  • the silver halide photographic emulsion which can be used in the present invention can be prepared by methods described in, for example, Research Disclosure (RD) No. 17643 (December 1978), pp. 22 to 23, "I. Emulsion preparation and types", RD No. 18716 (November 1979), page 648, and RD No. 307105 (November 1989), pp. 863 to 865; P. Glafkides, "Chemie et Phisique Photographique", Paul Montel, 1967; G.F. Duffin, "Photographic Emulsion Chemistry", Focal Press, 1966; and V.L. Zelikman et al., “Making and Coating Photographic Emulsion", Focal Press, 1964.
  • Monodisperse emulsions described in, for example, U.S. Patents 3,574,628 and 3,655,394, and British Patent 1,413,748 are also preferred.
  • tabular grains having an aspect ratio of about 3 or more can be used in the present invention.
  • the tabular grains can be easily prepared by methods described in, e.g., Gutoff, "Photographic Science and Engineering", Vol. 14, PP. 248 to 257 (1970); U.S. Patents 4,434,226; 4,414,310; 4,433,048 and 4,499,520, and British Patent 2,112,157.
  • the crystal structure may be uniform, may have different halogen compositions in the interior and the surface thereof, or may be a layered structure.
  • silver halides having different compositions may be joined by an epitaxial junction, or a compound other than a silver halide such as silver rhodanide or zinc oxide may be joined.
  • a mixture of grains having various types of crystal shapes may be used.
  • the above emulsion may be of any of a surface latent image type in which a latent image is mainly formed on the surface of each grain, an internal latent image type in which a latent image is formed in the interior of each grain, and a type in which a latent image is formed on the surface and in the interior of each grain.
  • the emulsion must be of a negative type.
  • the emulsion is of an internal latent image type, it may be a core/shell internal latent image type emulsion described in JP-A-63-264740. A method of preparing this core/shell internal latent image type emulsion is described in JP-A-59-133542.
  • the thickness of a shell of this emulsion changes in accordance with development or the like, it is preferably 3 to 40 nm, and most preferably, 5 to 20 nm.
  • a silver halide emulsion layer is normally subjected to physical ripening, chemical ripening, and spectral sensitization steps before it is used. Additives for use in these steps are described in RD Nos. 17,643; 18,716 and 307,105 and they are summarized in the table represented later.
  • two or more types of emulsions different in at least one of features such as a grain size, a grain size distribution, a halogen composition, a grain shape, and sensitivity can be mixed and used in the same layer.
  • colloidal silver can be preferably used in a light-sensitive silver halide emulsion layer and/or a substantially non-light-sensitive hydrophilic colloid layer.
  • the internally fogged or surface-fogged silver halide grains are silver halide grains which can be uniformly (non-imagewise) developed despite the presence of a non-exposed portion and exposed portion of the light-sensitive material.
  • a method of preparing the internally fogged or surface-fogged silver halide grain is described in U.S. Patent 4,626,498 or JP-A-59-214852.
  • the silver halides which form the core of the internally fogged or surface-fogged core/shell silver halide grains may be of the same halogen composition or different halogen compositions.
  • Examples of the internally fogged or surface-fogged silver halide are silver chloride, silver bromochloride, silver bromoiodide, and silver bromochloroiodide.
  • the grain size of these fogged silver halide grains is not particularly limited, an average grain size is preferably 0.01 to 0.75 ⁇ m, and most preferably, 0.05 to 0.6 ⁇ m.
  • the grain shape is also not particularly limited, and may be a regular grain shape.
  • the emulsion may be a polydisperse emulsion, it is preferably a monodisperse emulsion (in which at least 95% in weight or number of silver halide grains have a grain size falling within a range of ⁇ 40% of the average grain size).
  • Photographic emulsions used in the present invention may be subjected to spectral sensitization by methine dyes and the like.
  • Usable dyes include a cyanine dye, a merocyanine dye, a composite cyanine dye, a composite merocyanine dye, a holopolar cyanine dye. a hemicyanine dye, a styryl dye, and a hemioxonole dye. Most useful dyes are those belonging to a cyanine dye, a merocyanine dye, and a composite merocyanine dye. Any nucleus commonly contained as a basic heterocyclic nucleus in cyanine dyes can be contained in these dyes.
  • an applicable nucleus examples include a pyrroline uncleus, an oxazoline uncleus, a thiozoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, and pyridine nucleus; a nucleus in which an aliphatic hydrocarbon ring is fused to any of the above nuclei; and a nucleus in which an aromatic hydrocarbon ring is fused to any of the above nuclei, e.g., an indolenine nucleus, a benzindolenine uncleus, an indole nucleus, a benzoxazble nucleus, a naphthoxazole nucleus, a benzthiazole nucleus, a naphthothiazole nucleus, a benzoselen
  • a merocyanine dye or a composite merocyanine dye it is possible for a merocyanine dye or a composite merocyanine dye to have a 5- to 6-membered heterocyclic nucleus as a nucleus having a ketomethylene structure.
  • a pyrazolin-5-one nucleus a thiohydantoin nucleus, a 2-thiooxazolidin-2,4-dione nucleus, a thiazolidin-2,4-dione nucleus, a rhodanine nucleus, and a thiobarbituric acid nucleus.
  • sensitising dyes may be used singly, they can also be used together.
  • the combination of sensitising dyes is often used for a supersensitization purpose. Representative examples of the combination are described in U.S. Patents 2,688,545, 2,977,299, 3,397,060, 3,522,052, 3,527,641, 3,617,293, 3,628,964.
  • the emulsions used in the present invention may contain, in addition to the sensitising dyes, dyes having no spectral sensitizing effect or substances not essentially absorbing visible light and presenting supersensitization.
  • the sensitizing dyes can be added to an emulsion at any point in preparation of an emulsion, which is conventionally known to be useful. Most ordinarily, the addition is performed after completion of chemical sensitization and before coating. However, it is possible to perform the addition at the same time as addition of chemical sensitizing dyes to perform spectral sensitization and chemical sensitization simultaneously, as described in U.S. Patents 3,628,969 and 4,225,666. It is also possible to perform the addition prior to chemical sensitization, as described in JP-A-58-113928, or before completion of formation of a silver halide grain precipitation to start spectral sensitization. Alternatively, as disclosed in U.S.
  • Patent 4,225,666 these dyes described above can be added separately: a portion of the dyes may be added prior to chemical sensitization, while the remaining portion is added after that. That is, the dyes can be added at any time during formation of silver halide grains, including the method disclosed in U.S. Patent 4,183,756.
  • the addition amount of the sensitizing dye may be 4 ⁇ 10 ⁇ 6 to 8 ⁇ 10 ⁇ 3 mole per mole of silver halide. However, for a more preferable silver halide grain size of 0.2 to 1.2 ⁇ m, an addition amount of about 5 ⁇ 10 ⁇ 5 to 2 ⁇ 10 ⁇ 3 mole per mole of silver halide is more effective.
  • a non-light-sensitive fine grain silver halide is preferably used.
  • the non-light-sensitive fine grain silver halide means silver halide fine grains not sensitive upon imagewise exposure for obtaining a dye image and essentially not developed in development.
  • the non-light-sensitive fine grain silver halide is preferably not fogged beforehand.
  • the fine grain silver halide contains 0 to 100 mol% of silver bromide and may contain silver chloride and/or silver iodide as needed. Preferably, the fine grain silver halide contains 0.5 to 10 mol% of silver iodide.
  • An average grain size (an average value of equivalent-circle diameters of projected areas) of the fine grain silver halide is preferably 0.01 to 0.5 ⁇ m, and more preferably, 0.02 to 0.2 ⁇ m.
  • the fine grain silver halide can be prepared by a method similar to a method of preparing normal light-sensitive silver halide. In this preparation, the surface of a silver halide grain need not be subjected to either chemical sensitization or spectral sensitization. However, before the silver halide grains are added to a coating solution, a known stabilizer such as a triazole compound, an azaindene compound, a benzothiazolium compound, a mercapto compound, or a zinc compound is preferably added.
  • This fine grain silver halide grain-containing layer preferably contains colloidal silver.
  • a coating silver amount of the light-sensitive material of the present invention is preferably 6.0 g/m2 or less, and most preferably, 4.5 g/m2 or less.
  • the light-sensitive material of the present invention preferably contains a mercapto compound described in U.S. Patents 4,740,454 and 4,788,132, JP-A-62-18539, and JP-A-1-283551.
  • the light-sensitive material of the present invention preferably contains compounds which release, regardless of a developed silver amount produced by the development, a fogging agent, a development accelerator, a silver halide solvent, or precursors thereof, described in JP-A-1-106052 .
  • the light-sensitive material of the present invention preferably contains dyes dispersed by methods described in International Disclosure WO 88/04794 and JP-A-1-502912 or dyes described in European Patent 317,308A, U.S. Patent 4,420,555, and JP-A-1-259358.
  • yellow couplers 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 European Patent 249,473A.
  • magenta coupler examples are preferably 5-pyrazolone type and pyrazoloazole type compounds, and more preferably, compounds described in, for example, U.S. Patents 4,310,619 and 4,351,897, European Patent 73,636, U.S. Patents 3,061,432 and 3,725,067, RD No. 24220 (June 1984), JP-A-60-33552, RD No. 24230 (June 1984), JP-A-60-43659, JP-A-61-72238, JP-A-60-35730, JP-A-55-118034, JP-A-60-18951, U.S. Patents 4,500,630; 4,540,654 and 4,556,630, and WO No. 88/04795.
  • Examples of a cyan coupler are phenol type and naphthol type ones. Of these, preferable are those described in, for example, 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; 4,343,011 and 4,327,173, West German Patent Laid-open Application 3,329,729, European Patents 121,365A and 249,453A, U.S.
  • the pyrazoloazole type couplers disclosed in JP-A-64-553, JP-A-64-554, JP-A-64-555 and JP-A-64-556, and imidazole type couplers disclosed in U.S. Patent 4,818,672 can be used as cyan coupler in the present invention.
  • Typical examples of a polymerized dye-forming coupler are described in, e.g., U.S. Patents 3,451,820; 4,080,211; 4,367,282; 4,409,320 and 4,576,910, British Patent 2,102,173, and European Patent 341,188A.
  • 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, European Patent 96,570, and West German Laid-open Patent Application No. 3,234,533.
  • a colored coupler for correcting unnecessary absorption of a colored dye are those described in RD No. 17643, VII-G, RD No. 30715, 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.
  • a coupler for correcting unnecessary absorption of a colored dye by a fluorescent dye released upon coupling described in U.S. Patent 4,774,181 or a coupler having a dye precursor group which can react with a developing agent to form a dye as a split-off group described in U.S. Patent 4,777,120 may be preferably used.
  • DIR couplers i.e., couplers releasing a development inhibitor
  • couplers releasing a development inhibitor are preferably those described in the patents cited in the above-described RD No. 17643, VII-F and RD No. 307105, VII-F, JP-A-57-151944, JP-A-57-154234, JP-A-60-184248, JP-A-63-37346, JP-A-63-37350, and U.S. Patents 4,248,962 and 4,782,012.
  • RD Nos. 11449 and 24241, and JP-A-61-201247 disclose couplers which release bleaching accelerator. These couplers effectively serve to shorten the time of any process that involves bleaching. They are effective, particularly when added to light-sensitive material containing tabular silver halide grains.
  • a coupler which imagewise releases a nucleating agent or a development accelerator are preferably those described in British Patents 2,097,140 and 2,131,188, JP-A-59-157638, and JP-A-59-170840.
  • compounds releasing e.g., a fogging agent, a development accelerator, or a silver halide solvent upon redox reaction with an oxidized form of a developing agent, described in JP-A-60-107029, JP-A-60-252340, JP-A-1-44940, and JP-A-1-45687, can also be preferably used.
  • Examples of other compounds 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 couplers described in, e.g., U.S. Patents 4,283,472, 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 restores color after being released described in European Patent 173,302A and 313,308A; a ligand releasing coupler described in, e.g., U.S. Patent 4,553,477; a coupler releasing a leuco dye described in JP-A-63-75747; and a coupler releasing a fluorescent dye described in U
  • the couplers for use in this invention can be introduced into the light-sensitive material by various known dispersion methods.
  • Examples of a high-boiling point organic solvent to be used in the oil-in-water dispersion method are described in, e.g., U.S. Patent 2,322,027.
  • Examples of a high-boiling point organic solvent to be used in the oil-in-water dispersion method and having a boiling point of 175°C or more at atmospheric pressure are phthalic esters (e.g., dibutylphthalate, dicyclohexylphthalate, di-2-ethylhexylphthalate, decylphthalate, bis(2,4-di-t-amylphenyl) phthalate, bis(2,4-di-t-amylphenyl) isophthalate, bis(1,1-di-ethylpropyl) phthalate), phosphate or phosphonate esters (e.g., triphenylphosphate, tricresylphosphate, 2-ethylhexyldiphenylphosphate,
  • An organic solvent having a boiling point of about 30°C or more, and preferably, 50°C to about 160°C can be used as an auxiliary solvent.
  • Typical examples of the auxiliary solvent are ethyl acetate, butyl acetate, ethyl propionate, methylethylketone, cyclohexanone, 2-ethoxyethylacetate, and dimethylformamide.
  • antiseptics and fungicides agent are preferably added to the color light-sensitive material of the present invention.
  • Typical examples of the antiseptics and the fungicides are phenethyl alcohol, and 1,2-benzisothiazolin-3-one, n-butyl p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol, and 2-(4-thiazolyl)benzimidazole, which are described in JP-A-63-257747, JP-A-62-272248, and JP-A-1-80941.
  • the present invention can be applied to various color light-sensitive materials.
  • the material are a color negative film for a general purpose or a movie, a color reversal film for a slide or a television, a color paper, a color positive film, and a color reversal paper.
  • a support which can be suitably used in the present invention is described in, e.g., RD. No. 17643, page 28, RD. No. 18716, from the right column, page 647 to the left column, page 648, and RD. No. 307105, page 879.
  • the sum total of film thicknesses of all hydrophilic colloidal layers at the side having emulsion layers is preferably 28 ⁇ m or less, more preferably, 23 ⁇ m or less, much more preferably, 18 ⁇ m or less, and most preferably, 16 ⁇ m or less.
  • a film swell speed T 1/2 is preferably 30 seconds or less, and more preferably, 20 seconds or less.
  • the film thickness means a film thickness measured under moisture conditioning at a temperature of 25°C and a relative humidity of 55% (two days).
  • the film swell speed T 1/2 can be measured in accordance with a known method in the art. For example, the film swell speed T 1/2 can be measured by using a swello-meter described by A.
  • T 1/2 is defined as a time required for reaching 1/2 of the saturated film thickness.
  • the film swell speed T 1/2 can be adjusted by adding a film hardening agent to gelatin as a binder or changing aging conditions after coating.
  • a swell ratio is preferably 150% to 400%.
  • the swell ratio is calculated from the maximum swell film thickness measured under the above conditions in accordance with a relation: (maximum swell film thickness - film thickness)/film thickness.
  • a hydrophilic colloid layer having a total dried film thickness of 2 to 20 ⁇ m is preferably formed on the side opposite to the side having emulsion layers.
  • the back layer preferably contains, e.g., the light absorbent, the filter dye, the ultraviolet absorbent, the antistatic agent, the film hardener, the binder, the plasticizer, the lubricant, the coating aid, and the surfactant, described above.
  • the swell ratio of the back layer is preferably 150% to 500%.
  • the color photographic light-sensitive material according to the present invention can be developed by conventional methods described in RD. No. 17643, pp. 28 and 29, RD. No. 18716, the left to right columns, page 651, and RD. No. 307105, pp. 880 and 881.
  • a color developer used in development of the light-sensitive material of the present invention is an aqueous alkaline solution containing as a main component, preferably, an aromatic primary amine color developing agent.
  • an aromatic primary amine color developing agent preferably, an aminophenol compound is effective, a p-phenylenediamine compound is preferably used.
  • Typical examples of the p-phenylenediamine compound are: 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -methoxyethylaniline, 4-amino-3-methyl-N-methyl-N-(3-hydroxypropyl)aniline, 4-amino-3-methyl-N-ethyl-N-(3-hydroxypropyl)aniline, 4-amino-3-methyl-N-ethyl-N-(2-hydroxypropyl)anline, 4-amino-3-ethyl-N-ethyl-N-(3-hydroxypropyl)aniline, 4-amino-3-methyl-N-propyl-N
  • 3-methyl-4-amino-N-ethyl-N- ⁇ -hydroxyethylaniline, 4-amino-3-methyl-N-ethyl-N-(3-hydroxypropyl)aniline, 4-amino-3-methyl-N-ethyl-N-(4-hydroxybutyl)aniline, and the sulfates, hydrochlorides and p-toluenesulfonates thereof are preferred in particular.
  • the above compounds can be used in a combination of two or more thereof in accordance with the application.
  • the color developer contains a pH buffering agent such as a carbonate, a borate or a phosphate of an alkali metal, and a development restrainer or an antifoggant such as a chloride, a bromide, an iodide, a benzimidazole, a benzothiazole, or a mercapto compound.
  • a pH buffering agent such as a carbonate, a borate or a phosphate of an alkali metal
  • an antifoggant such as a chloride, a bromide, an iodide, a benzimidazole, a benzothiazole, or a mercapto compound.
  • the color developer may also contain a preservative such as hydroxylamine, diethylhydroxylamine, a sulfite, a hydrazine such as N,N-biscarboxymethylhydrazine, a phenylsemicarbazide, triethanolamine, or a catechol sulfonic acid; an organic solvent such as ethyleneglycol or diethyleneglycol; a development accelerator such as benzylalcohol, polyethyleneglycol, a quaternary ammonium salt or an amine; a dye-forming coupler; a competing coupler; an auxiliary developing agent such as 1-phenyl-3-pyrazolidone; a viscosity-imparting agent; and a chelating agent such as an aminopolycarboxylic acid, an aminopolyphosphonic acid, an alkylphosphonic acid, or a phosphonocarboxylic acid.
  • a preservative such as hydroxylamine, diethylhydroxylamine, a
  • the chelating agent examples include ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid, and ethylenediamine-di(o-hydroxyphenylacetic acid), and salts thereof.
  • black-and-white development is performed and then color development is performed.
  • a black-and-white developer a well-known black-and-white developing agent, 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 a combination of two or more thereof.
  • the pH of the color and black-and-white developers is generally 9 to 12.
  • the quantity of replenisher of the developers depends on a color photographic light-sensitive material to be processed, it is generally 3 liters or less per m2 of the light-sensitive material.
  • the quantity of replenisher can be decreased to be 500 ml or less by decreasing a bromide ion concentration in a replenisher.
  • a contact area of a processing tank with air is preferably decreased to prevent evaporation and oxidation of the solution upon contact with air.
  • the above aperture is preferably 0.1 or less, and more preferably, 0.001 to 0.05.
  • a shielding member such as a floating cover may be provided on the surface of the photographic processing solution in the processing tank.
  • a method of using a movable cover described in JP-A-1-82033 or a slit developing method descried in JP-A-63-216050 may be used.
  • the aperture is preferably reduced not only in color and black-and-white development steps but also in all subsequent steps, e.g., bleaching, bleach-fixing, fixing, washing, and stabilizing steps.
  • the quantity of replenisher can be reduced by using a means of suppressing storage of bromide ions in the developing solution.
  • a color development time is normally 2 to 5 minutes.
  • the processing time can be shortened by setting a high temperature and a high pH and using the color developing agent at a high concentration.
  • the photographic emulsion layer is generally subjected to bleaching after color development.
  • the bleaching may be performed either simultaneously with fixing (bleach-fixing) or independently thereof.
  • bleach-fixing may be performed after bleaching.
  • processing may be performed in a bleach-fixing bath having two continuous tanks, fixing may be performed before bleach-fixing, or bleaching may be performed after bleach-fixing, in accordance with the application.
  • the bleaching agent are compounds of a polyvalent metal, e.g., iron (III); peracids; quinones; and nitro compounds.
  • Typical examples of the bleaching agent are an organic complex salt of iron (III), e.g., a complex salt with an aminopolycarboxylic acid such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, and 1,3-diaminopropanetetraacetic acid, and glycoletherdiaminetetraacetic acid; or a complex salt with citric acid, tartaric acid, or malic acid.
  • an aminopolycarboxylic acid such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, and 1,3-diaminopropanetetraacetic acid, and glycoletherdiaminetetraacetic acid
  • a complex salt with citric acid, tartaric acid, or malic acid e.g
  • an iron (III) complex salt of an aminopolycarboxylic acid such as an iron (III) complex salt of ethylenediaminetetraacetic acid or 1,3-diaminopropanetetraacetic acid is preferred because it can increase a processing speed and prevent an environmental contamination.
  • the iron (III) complex salt of an aminopolycarboxylic acid is useful in both the bleaching and bleach-fixing solutions.
  • the pH of the bleaching or bleach-fixing solution using the iron (III) complex salt of an aminopolycarboxylic acid is normally 4.0 to 8. In order to increase the processing speed, however, processing can be performed at a lower pH.
  • a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution, and their pre-bath, if necessary.
  • a useful bleaching accelerator are: compounds having a mercapto group or a disulfide group described in, for example, U.S.
  • Patent 3,893,858 West German Patents 1,290,812 and 2,059,988, JP-A-53-32736, JP-A-53-57831, JP-A-53-37418, JP-A-53-72623, JP-A-53-95630, JP-A-53-95631, JP-A-53-104232, JP-A-53-124424, JP-A-53-141623, JP-A-53-28426, and RD No.
  • a compound having a mercapto group or a disulfide group is preferable since the compound has a large accelerating effect.
  • Patent 3,893,858, West German Patent 1,290,812, and JP-A-53-95630 are preferred.
  • a compound described in U.S. Patent 4,552,834 is also preferable.
  • These bleaching accelerators may be added in the light-sensitive material. These bleaching accelerators are useful especially in bleach-fixing of a photographic color light-sensitive material.
  • the bleaching solution or the bleach-fixing solution preferably contains, in addition to the above compounds, an organic acid in order to prevent a bleaching stain.
  • the most preferable organic acid is a compound having an acid dissociation constant (pKa) of 2 to 5, e.g., acetic acid, propionic acid, or hydroxy acetic acid.
  • Examples of the fixing agent used in the fixing solution or the bleach-fixing solution are a thiosulfate salt, a thiocyanate salt, a thioether-based compound, a thiourea and a large amount of an iodide.
  • a thiosulfate especially, ammonium thiosulfate, can be used in the widest range of applications.
  • a combination of a thiosulfate with a thiocyanate, a thioether-based compound or thiourea is preferably used.
  • a sulfite, a bisulfite, a carbonyl bisulfite adduct, or a sulfinic acid compound described in European Patent 294,769A is preferred.
  • various types of aminopolycarboxylic acids or organic phosphonic acids are preferably added to the solution.
  • 0.1 to 10 moles, per liter, of a compound having a pKa of 6.0 to 9.0 are preferably added to the fixing solution or the bleach-fixing solution in order to adjust the pH.
  • a compound having a pKa of 6.0 to 9.0 are preferably added to the fixing solution or the bleach-fixing solution in order to adjust the pH.
  • the compound are imidazoles such as imidazole, 1-methylimidazole, 1-ethylimidazole, and 2-methylimidazole.
  • the total time of a desilvering step is preferably as short as possible as long as no desilvering defect occurs.
  • a preferable time is one to three minutes, and more preferably, one to two minutes.
  • a processing temperature is 25°C to 50°C, and preferably, 35°C to 45°C. Within the preferable temperature range, a desilvering speed is increased, and generation of a stain after the processing can be effectively prevented.
  • stirring is preferably as strong as possible.
  • a method of intensifying the stirring are a method of colliding a jet stream of the processing solution against the emulsion surface of the light-sensitive material described in JP-A-62-183460, a method of increasing the stirring effect using rotating means described in JP-A-62-183461, a method of moving the light-sensitive material while the emulsion surface is brought into contact with a wiper blade provided in the solution to cause disturbance on the emulsion surface, thereby improving the stirring effect, and a method of increasing the circulating flow amount in the overall processing solution.
  • Such a stirring improving means is effective in any of the bleaching solution, the bleach-fixing solution, and the fixing solution.
  • the above stirring improving means is more effective when the bleaching accelerator is used, i.e., significantly increases the accelerating speed or eliminates fixing interference caused by the bleaching accelerator.
  • An automatic developing machine for processing the light-sensitive material of the present invention preferably has a light-sensitive material conveyer means described in JP-A-60-191257, JP-A-60-191258, or JP-A-60-191259.
  • this conveyer means can significantly reduce carry-over of a processing solution from a pre-bath to a post-bath, thereby effectively preventing degradation in performance of the processing solution. This effect significantly shortens especially a processing time in each processing step and reduces the quantity of replenisher of a processing solution.
  • the photographic light-sensitive material of the present invention is normally subjected to washing and/or stabilizing steps after desilvering.
  • An amount of water used in the washing step can be arbitrarily determined over a broad range in accordance with the properties (e.g., a property determined by the substances used, such as a coupler) of the light-sensitive material, the application of the material, the temperature of the 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 Engineering", Vol. 64, PP. 248 - 253 (May, 1955).
  • a germicide such as an isothiazolone compound and a 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 et al., "Chemistry of Antibacterial and Antifungal Agents", (1986), Sankyo Shuppan, Eiseigijutsu-Kai ed., “Sterilization, Antibacterial, and Antifungal Techniques for Microorganisms", (1982), Kogyogijutsu-Kai, and Nippon Bokin Bobai 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 light-sensitive material of the present invention can be processed directly by a stabilizing agent in place of water-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 processing.
  • stabilizing is performed subsequently to washing.
  • An example is a stabilizing bath containing a dye stabilizing agent and a surface-active agent to be used as a final bath of the photographic color light-sensitive material.
  • the dye stabilizing agent are an aldehyde such as formalin or glutaraldehyde, an N-methylol compound, hexamethylenetetramine, and an adduct of aldehyde sulfite.
  • Various chelating agents and fungicides can be added to the stabilizing bath.
  • An overflow solution produced upon washing and/or replenishment of the stabilizing solution can be reused in another step such as a desilvering step.
  • the silver halide color light-sensitive material of the present invention may contain a color developing agent in order to simplify processing and increases a processing speed.
  • a color developing agent for this purpose, various types of precursors of a color developing agent can be preferably used.
  • the precursor are an indoaniline-based compound described in U.S. Patent 3,342,597, Schiff base compounds described in U.S. Patent 3,342,599 and RD Nos. 14850 and 15159, an aldol compound described in RD No. 13924, a metal salt complex described in U.S. Patent 3,719,492, and a urethane-based compound described in JP-A-53-135628.
  • the silver halide color light-sensitive material of the present invention may contain various 1-phenyl-3-pyrazolidones in order to accelerate color development, if necessary.
  • Typical examples of the compound are described in JP-A-56-64339, JP-A-57-144547, and JP-A-58-115438.
  • Each processing solution in the present invention is used at a temperature of 10°C to 50°C. Although a normal processing temperature is 33°C to 38°C, processing may be accelerated at a higher temperature to shorten a processing time, or image quality or stability of a processing solution may be improved at a lower temperature.
  • the number corresponding to each component indicates the coating amount in units of g/m2.
  • the coating amount of a silver halide is represented by the amount of silver.
  • the coating amount of each sensitizing dye is represented in units of mols per mol of silver halide in the same layer.
  • the individual layers contained W-1 to W-3, B-4 to B-6, F-1 to F-17, iron salt, and lead salt.
  • Each of the film samples 11 and 12 was formed into a 135-format cartridge of 24 exposures, and moisture-conditioned at a temperature of 25°C and a relative humidity of 60%. Thereafter, these film samples were loaded in perfectly light-shielding cartridges, and then sealed in transparent sealing cases and light-shielding sealing cases, in a dark place, to prepare encased photographic product samples 101 to 108 as shown in Table 3 below.
  • the ratio of the film area loaded in the cartridge so as to be shielded from light to the film area extracted from a film extraction portion was 1 : 0.05.
  • One group of these product samples 101 to 108 was irradiated with light of 10,000 lux for 24 hours and preserved, together with the other group not irradiated with light, at 60°C and a relative humidity of 60% for three days. Thereafter, the films were processed under the following conditions.
  • compositions of the individual processing solutions are shown below.
  • Tap water was supplied to a mixed-bed column filled with an H type strongly acidic cation exchange resin (Amberlite IR-120B: available from Rohm & Haas Co.) and an OH type strongly basic anion exchange resin (Amberlite IR-400) to set the concentrations of calcium and magnesium to be 3 mg/l or less. Subsequently, 20 mg/l of isocyanuric acid dichloride sodium salt and 150 mg/l of sodium sulfate were added. The pH of the solution ranged from 6.5 to 7.5.
  • the shielded portion of the processed film was cut, and sensitometry was performed.
  • a film sample 21 was made following the same procedures as for the film sample 12 except 0.07, 0.015, and 0.02 g/m2 of Cpd-3 were added to the 11th, 12th, and 13th layers, respectively.
  • Encased product samples 201 and 202 were prepared from the film sample 12 and 21, respectively, following the same procedures as in Example 1, and subjected to the same experiment and processing as in Example 1. The results are shown in Table 4 below.
  • Water-soluble dyes ExF-1 to ExF-3 indicated below, were added to the 14th layer of the film sample 11 in an amount sufficient to lower the ISO sensitivity of the film sample 11 from 435 to 120, to prepare a film sample 31, and also in an amount sufficient to lower the ISO sensitivity of the film sample 11 from 435 to 50, to prepare a film sample 32.
  • the sample 101 was subjected to the experiment and the processing following the same procedures as in Example 1 under different humidity conditions. The results are summarized in Table 6 below.
  • Encased product samples 501 to 508 were prepared, corresponding to the encased product samples 101 to 108 prepared in Example 1, and the same experiment was conducted as in Example 1, except that the samples were processed with the following black-and-white development, using an automatic developing machine. Processing solution Temperature Time Development HPD 26.5°C 55 sec. Fixing Super Fujix DPZ 26.5°C 76 sec. Washing Flowing Water 20°C 95 sec. Drying 50°C 69 sec.
  • Film samples 61 to 64 were prepared by the same procedures as for the film sample 12, except that the amount of tetrachloropalladium (II) potassium was changed as shown in Table 8 below.
  • Each of the film samples 61 to 64 was formed into a 135-format cartridge of 24 exposures, and moisture-conditioned at a temperature of 25°C and a relative humidity of 60%. Then, these samples ware sealed in transparent cases, to prepare encased product samples 601 to 616.
  • the ratio of the extracted film area to the film area loaded in the cartridge was as shown in Table 8.
  • abnormal fog does not occur in the samples having no extracted film portion, and abnormal fog decreases as the amount of hydrogen cyanide gas scavenger increases with respect to thiocyanate salt. Further, it is seen that the degree of increase of fog becomes the same as the sample without an extracted film portion when the amount of hydrogen cyanide gas scavenger is more than 1.0 mol per mol of thiocyanate salt, completely solving the abnormal fog problem.
  • Film samples 71 to 74 were prepared by adding the exemplified compound Y-6 in an amount of 0.01 g/m2 to the 10th layer of the film sample 12 of Example 1, with the amount of hydrogen cyanide gas scavenger, tetrachloropalladium (II) potassium, varied as shown in Table 9 below.
  • Each of the film samples 71 to 74 was formed into a 135-format cartridge of 24 exposures, and moisture-conditioned at a temperature of 25°C and a relative humidity of 60%. Then these samples were sealed in transparent cases to prepare encased product samples 701 to 704. The ratio of the extracted film area to the shielded film area wat set at 0.05.
  • Emulsion I is a diagrammatic representation of Emulsion I:
  • spectral sensitizing dyes ExS-4, ExS-5 and ExS-6 to be used in the 9th layer of the film sample 81 which will be described later, and optimal chemical sensitization as described below was performed to prepare emulsions 1 and 2.
  • the optimal sensitization means that, after the sensitization, the highest sensitivity is achieved when exposed for 1/100 second.
  • Emulsion 1 gold-sulfur sensitization
  • Optimal chemical sensitization was performed at 56°C by using 2.2 ⁇ 10 ⁇ 3 mole of sodium thiocyanate, 1.5 ⁇ 10 ⁇ 6 mole of chloroauric acid and 1.4 ⁇ 10 ⁇ 5 mole of sodium thiosulfate, per mole of silver halide.
  • Emulsion 2 gold-sulfur-selenium sensitization
  • Optimal chemical sensitization was performed at 56°C by using 2.2 ⁇ 10 ⁇ 3 mole of sodium thiocyanate, 2.2 ⁇ 10 ⁇ 6 mole of chloroauric acid, 1.0 ⁇ 10 ⁇ 5 mole of sodium thiosulfate and a selenium sensitizer (the exemplified compound 40), per mole of silver halide.
  • the number corresponding to each component indicates the coating amount in units of g/m2.
  • the coating amount of a silver halide is represented by the amount of silver.
  • the coating amount of each sensitizing dye is represented in units of mols per mol of silver halide in the same layer.
  • the individual layers contained W-1 to W-3, B-4 to B-6, F-1 to F-17, iron salt, and lead salt.
  • a film sample 82 was made following the same procedures as for the film sample 81 except the emulsions 1 in the 9th layer of the film sample 82 was replaced with the emulsion 2.
  • Each of the film samples 81 and 82 contained 3 ⁇ 10 ⁇ 3 mol of thiocyanate salt per mol of silver.
  • the thiocyanate salt had been used in preparing the emulsions A to G, and 1 and 2.
  • Film samples 83 and 84 were made following the same procedures as for the film samples 81 and 82 except 1 ⁇ 10 ⁇ 5 mol/molAg, as a total silver amount, of sodium palladium(II) chloride was added to the sixth layers (interlayer) of the film samples 81 and 82, respectively.
  • Film samples 85 and 86 were made following the same procedures as for the film samples 81 and 82 except 1 ⁇ 10 ⁇ 5 mol/molAg, as a total silver amount, of sodium palladium(II) chloride was added to the sixth layers (interlayer) of the film samples 81 and 82, respectively.
  • Each of the film samples 81 to 86 was formed into a 135-format cartridge of 24 exposures, and moisture-conditioned at a temperature of 25°C and a relative humidity of 60%. Thereafter, these film samples were placed in transparent cartridge cases and perfectly light-shielding cartridge cases in a dark place, to prepare encased product samples 801 to 812 as shown in Table 10 below.
  • the ratio of the film area loaded in the cartridge so as to be shielded from light to the film area extracted from a film extraction portion was 1 : 0.05.
  • the density of the processed samples was measured with a green filter, and an increase in fog and a change in sensitivity were determined for the samples preserved at a temperature of 60°C and a relative humidity of 60%.
  • the results are shown in Table 11 below.
  • the change in sensitivity is expressed as a relative logarithmic value of the exposure amount required to obtain an optical density of fog plus 0.15, with the sensitivity of the encased samples without irradiation of light and preserved at a temperature of 25°C and a relative humidity of 60% taken as 100.
  • Cpd-3 was added in an amount of 0.07, 0.015, and 0.02 g/m2, respectively, to prepare a film sample 87.
  • Encased product samples 814 to 821 were prepared by the same procedures as in Example 8, except that the moisture-conditioning was performed under different conditions as described in Table 13 below. These product samples were subjected to the same experiment as in Example 8. The results are shown also in Table 13.
  • Example 8 The same experiment was performed on the encased samples 801 to 812 as in Example 8, except that the samples were processed with the following black-and-white development instead of the color development. As a result, it was confirmed that no remarkable abnormal fog did not occur. Therefore, the effect of the present invention is more significant when the light-sensitive material is processed by color development.
  • the samples were developed using the above developer, and stopping, fixing, washing and drying were performed by the conventional method.

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  • General Physics & Mathematics (AREA)
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  • Microelectronics & Electronic Packaging (AREA)
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EP93108613A 1992-05-27 1993-05-27 In einer Filmkapsel verpacktes photographischen Material. Withdrawn EP0572022A3 (de)

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JP15896392A JPH05333480A (ja) 1992-05-27 1992-05-27 ハロゲン化銀写真製品
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Cited By (5)

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US5614360A (en) * 1994-12-16 1997-03-25 Eastman Kodak Company Photographic element and coating composition
US5650265A (en) * 1995-12-22 1997-07-22 Eastman Kodak Company Silver halide light-sensitive element
EP0945755A1 (de) * 1998-03-25 1999-09-29 Agfa-Gevaert N.V. Bildaufzeichnungselement, das Silberhalogenidkristalle enthält, die im Inneren mit einem Metall-Halogen-Fluor-Komplex modifiziert sind
EP0967520A1 (de) * 1998-06-25 1999-12-29 Eastman Kodak Company Farbphotographisches Negativmaterial mit modifizierter Verteilung des Fängers für Entwickleroxidationsprodukt
US6284450B1 (en) 1998-03-25 2001-09-04 Agfa-Gevaert Photosensitive image-forming element containing silver halide crystals internally modified with a metal-halogen-fluorine-complex

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US4827298A (en) * 1987-02-09 1989-05-02 Fuji Photo Film Co., Ltd. Photographic light-sensitive material-packed unit having exposure function
WO1989012847A1 (en) * 1988-06-20 1989-12-28 Eastman Kodak Company Photographic material protected against hydrogen cyanide gas
EP0439069A2 (de) * 1990-01-19 1991-07-31 Fuji Photo Film Co., Ltd. Lichtempfindliches photographisches Silberhalogenidmaterial
GB2243362A (en) * 1987-12-01 1991-10-30 Fuji Photo Film Co Ltd Photographic film package
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US3553243A (en) * 1966-04-05 1971-01-05 American Cyanamid Co Method of inhibiting evolution of hydrogen cyanide from organic thiocyanate compositions
US4827298A (en) * 1987-02-09 1989-05-02 Fuji Photo Film Co., Ltd. Photographic light-sensitive material-packed unit having exposure function
GB2243362A (en) * 1987-12-01 1991-10-30 Fuji Photo Film Co Ltd Photographic film package
WO1989012847A1 (en) * 1988-06-20 1989-12-28 Eastman Kodak Company Photographic material protected against hydrogen cyanide gas
US5112733A (en) * 1989-05-31 1992-05-12 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
EP0439069A2 (de) * 1990-01-19 1991-07-31 Fuji Photo Film Co., Ltd. Lichtempfindliches photographisches Silberhalogenidmaterial

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5614360A (en) * 1994-12-16 1997-03-25 Eastman Kodak Company Photographic element and coating composition
US5650265A (en) * 1995-12-22 1997-07-22 Eastman Kodak Company Silver halide light-sensitive element
EP0945755A1 (de) * 1998-03-25 1999-09-29 Agfa-Gevaert N.V. Bildaufzeichnungselement, das Silberhalogenidkristalle enthält, die im Inneren mit einem Metall-Halogen-Fluor-Komplex modifiziert sind
US6284450B1 (en) 1998-03-25 2001-09-04 Agfa-Gevaert Photosensitive image-forming element containing silver halide crystals internally modified with a metal-halogen-fluorine-complex
EP0967520A1 (de) * 1998-06-25 1999-12-29 Eastman Kodak Company Farbphotographisches Negativmaterial mit modifizierter Verteilung des Fängers für Entwickleroxidationsprodukt
US6043012A (en) * 1998-06-25 2000-03-28 Eastman Kodak Company Color negative photographic elements with modified scavenging compound distributions

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