Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/04—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with macromolecular additives; with layer-forming substances
  • G03C1/043—Polyalkylene oxides; Polyalkylene sulfides; Polyalkylene selenides; Polyalkylene tellurides
• • 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
• • 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

• Japanese Pat. publication No. 4,935/68 discloses a process for preventing a photograhie emulsion from high intensity reciprocity law failure by incorporation of iridium salt into the photographic emulsion
• Japanese Pat. publication No. 32.738/70 discloses a process in which the process of said Japanese Patv publication No. 4,935/68 has been improved by use of gold salt in combination with iridium salt.
• the present invention is a process which is of greater excellent in effect than the said prior art processes, and hence may be said to be an entirely novel invention. That is, the present invention is a process for preventing a silver halide photographic emulsion from said high intensity reciprocity law failure by incorporating into the photographic emulsion a gold salt in combination with a polyalkylene oxide or a derivative thereof and. preferably, with at least one member selected from the group consisting of soluble salts of metals such as cadmium. zinc, cobalt, nickel, thallium, uranium. thorium, iridium, strontium and lead.
• the reciprocity law failure the complete prevention of which has heretofore been difficult, can be prevented substantially ideally from the practical standpoint.
• the incorporation of a gold salt into a silver halide photograhic emulsion which is a sensitization procedure known as gold sensitization is known to provide prominent effect of preventing the emulsion from reciprocity failure, particularly from high intensity reciprocity failure.
• the effect attained by incorporation of gold salt is far more excellent than that attained by incorporation of iridium salt.
• polyalkylene oxides synthetic with polyalkylene glycols
• derivatives thereof may be shown as wellknown sensitizers. The present inventors have found that the said compounds also have the effect of preventing the reciprocity law failure, particularly the failure caused at the time of high intensity and short period exposure.
• a photographic material containing in the silver halide photographic emulsion layer a polyethylene oxide, which has ordinarily been used as a sensitizer is higher in sensitivity than a photograhic material containing no polyethylene oxide.
• This effect is marked when the photographic material is exposed to a higher intensity light for a shorter period of time, and the sensitization at the shoulder portion of characteristic curve of the photographic material is particularly marked, with the result that the high illuminance reciprocity law failure can be prevented.
• the above-mentioned effect is identical in tendency with that of a gold salt.
• the present inventors have confirmed that the prevention of high intensity reciprocity law failure can be accomplished to an extremely desirable extent by use of a gold salt in combination with a polyalkylene oxide.
• the inventors have further found that an ideal effect, which is substantially satisfactory from the practical standpoint, can be obtained when said gold salt and polyalkylene oxide are used in further combination with a soluble salt of cadmium, zinc, cobalt, nickel, thallium, uranium, thorium, iridium, strontium, lead or the like metal other than gold.
• the polyalkylene oxides referred to herein are generally used polyethylene oxides having molecular weights in the range from 400 to 10,000.
• the scope of the present invention is not limited thereto, and the same effects as above can be obtained even when other polyalkylene oxides and derivatives thereof are used. That is, condensation products (molecular weight 600 to 10,000) of alkylene oxides with at least one member selected from the group consisting of water, aliphatic alcohols, glycols, fatty acids, aliphatic amines, phenols, and dehydrated cyclic compounds of hcxitol derivatives also display the same ef fects as above, and it is needless to say that all the said compounds are involved in the scope of the present invention.
• soluble metal salts other than the gold salts are desirably used, in practice, in the form of halides, nitrates or sulfates, though this is, of course, not limitative.
• the proportions of the individual materials used in the present invention vary depending on the kinds thereof, but are preferably such that the gold salt is used in a proportion of 0.1 to 200 mg., preferably 5 to 50 mg., in terms of gold atom, per mole of silver halide, the polyalkylene oxide in a proportion of 0.1 to 50 g, per mole of silver halide, and the soluble metal salt other than the gold salt in a proportion of 10 mg. to 50 g per mole of silver halide.
• These materials may be incorporated into a photographic emulsion at such stages that the gold salt and the metal salt other than gold salt may be incorporated at any stage of emulsification, first ripening, second ripening or after completion of ripen ing, and the polyalkylene oxide may be incorporated at any stage of second ripening or after completion of ripening.
• EXAMPLE I A silver iodobromide emulsion containing 2% of silver iodide, which had been prepared according to a process known to those skilled in the art, was washed with water and then subjected to second ripening. In this case, one half of the emulsion was subjected to only sulfur sensitization (emulsion A), and the remainder was incorporated with 20 mg. per mole of silver halide of gold thiocyanate in terms of gold. The thus treated emulsions were individually adjusted to a pH of 6.0 and ripened at 50C. for 90 minutes. Further, the latter emulsion was equally divided into 4 emulsions.
• emulsion B the second emulsion was incorporated with l g. per mole of silver halide of polyethylene oxide having a molecular weight of 6,000
• emulsion C the third emulsion was incorporated with 3 g. per mole of silver halide of cobalt chloride
• emulsion E the fourth emulsion was incorporated with l g. per mole of silver halide of polyethylene oxide in combination with 3 g. per mole of silver halide of cobalt chloride
• EXAMPLE 2 A silver iodochlorobromide emulsion containing 30 mole% of silver bromide and a slight amount of silver iodide was washed with water and then subjected to second ripening. In this case, one half of the emulsion was subjected to only sulfur sensitization (emulsion F), and the remainder was incorporated with 50 mg. per mole of silver halide of gold chloride in terms of gold. The thus treated emulsions were individually adjusted to a pH of5.5 and ripened for 60 minutes.
• the latter emulsion was equally divided into 4 emulsions, and the first emulsion was left as it was (emulsion G), the second emulsion was incorporated with 0.5 g. per mole of silver halide of polyethylene glycol having a molecular weight of 2,000 (emulsion H), the third emulsion was incorporated with l g. per mole of silver halide of strontium chloride (emulsion l), and the fourth emulsion was incorporated with 0.5 g. per mole of silver halide of polyethylene glycol and l g. per mole of silver halide of strontium chloride (emulsion J).
• the present process for preparing improved silver halide photographic emulsions does not disturb the effects of other sensitization processes. e.g. reduction sensitization and spectral sensitization (including supersensitizution and hence may be adopted in combination with said processes. Further, the same effects as mentioned above can be obtained even when the present process is applied to emulsions containing color couplers.
• a method for producing a silver halide photographic emulsion suitable for preventing high intensity reciprocity law failure which consists essentially of adding to a silver halide photographic emulsion either (1) a gold salt or (2) a mixture of l and at least one soluble salt selected from the group consisting of halide, nitrate and sulfate salts of cadmium, zinc, cobalt, nickel, thallium, uranium, thorium, iridium, strontium and lead at a stage ranging from emulsification to after completion of ripening and adding a polyalkylene oxide or condensation product thereof with water, aliphatic alcohol, glycol, fatty acid, aliphatic amine, or dehydrated cyclic hexitol compounds at a stage ranging from second ripening to after completion of ripening.
• polya1 kylene oxide or condensation product thereof is polyethylene oxide.

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• Physics & Mathematics (AREA)
• Chemical & Material Sciences (AREA)
• Spectroscopy & Molecular Physics (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• General Physics & Mathematics (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)

Applications Claiming Priority (1)

Publications (1)

Family

ID=13911365

Family Applications (1)

Country Status (3)

Cited By (16)

Families Citing this family (1)

Citations (11)

Family Cites Families (7)

• 1972
  • 1972-08-31 JP JP47087314A patent/JPS5232569B2/ja not_active Expired
• 1973
  • 1973-08-17 US US389153A patent/US3901711A/en not_active Expired - Lifetime
  • 1973-08-24 DE DE2342905A patent/DE2342905C2/de not_active Expired

Patent Citations (11)

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